WO2013102533A1 - Matériaux, production et utilisation desdits matériaux - Google Patents

Matériaux, production et utilisation desdits matériaux Download PDF

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Publication number
WO2013102533A1
WO2013102533A1 PCT/EP2012/074976 EP2012074976W WO2013102533A1 WO 2013102533 A1 WO2013102533 A1 WO 2013102533A1 EP 2012074976 W EP2012074976 W EP 2012074976W WO 2013102533 A1 WO2013102533 A1 WO 2013102533A1
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Prior art keywords
electrochemical cells
present
material according
general formula
electrodes
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PCT/EP2012/074976
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German (de)
English (en)
Inventor
Martin Schulz-Dobrick
Aleksei Volkov
Simon SCHRÖDLE
Jordan Keith Lampert
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Basf Se
Basf Schweiz Ag
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Publication of WO2013102533A1 publication Critical patent/WO2013102533A1/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
    • H01M4/02—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

  • 0.2 ⁇ a ⁇ 0.5, 0.0 ⁇ b ⁇ 0.4, 0.4 ⁇ c ⁇ 0.65, 1, 1 ⁇ x ⁇ 1, 3, x + a + b + c - 0, 2 ⁇ z ⁇ x + a + b + c + 0.2 and a + b + c 1 where c / a is 1, 2, and wherein the material has a BET surface area of at least 3 m 2 / g.
  • the present invention relates to a process for the preparation of materials according to the invention and their use as or in electrode materials. Furthermore, the present invention relates to electrodes containing at least one electrode material according to the invention. Furthermore, the present invention relates to electrochemical cells containing at least one electrode according to the invention.
  • Electrochemical cells which have a high storage capacity at the highest possible working voltage, are of increasing importance.
  • the desired capacities are generally not achievable with electrochemical cells which work on the basis of aqueous systems.
  • lithium-ion batteries charge transport is not ensured by protons in more or less hydrated form, but by lithium ions in a non-aqueous solvent or in a non-aqueous solvent system. A special role is played by the electrode material.
  • NCM compounds described so far are oxidic compounds characterized by a molar ratio of lithium to transition metals of about 1.00 to 1.15 and a manganese content of about 15 mol% to 45 mol%, based on the sum of the transition metals (Ni, Co and Mn).
  • the high energy NCM compounds have discharge capacities of up to 300 mAh / g when cycled between 2.0 V and 4.6 V versus elemental lithium.
  • the advantage of high energy NCM compounds over standard NCM compounds is that high energy NCM compounds have higher energy density and are more stable cycling up to 4.6V.
  • the disadvantage is that the average discharge voltage is below 3.5 V and that it drops by 0.1 V to 0.4 V when cycling high-energy NCM compounds.
  • a technical problem with the use of cathode materials in batteries may arise when the voltage range in which the capacitance is delivered is very low and / or changes from cycle to cycle, especially as it decreases. This lowering of the voltage is undesirable because it lowers the energy density and makes it difficult to determine the state of charge of the battery by measuring the voltage.
  • Another object was to provide a process for producing materials having the properties described above.
  • Another object was to provide combinations for materials having the properties described above.
  • "cycling" and “cycling” are used with the same meaning and designate the charging and discharging of batteries or of electrochemical cells. Accordingly, the initially defined materials of the general formula (I) were found which have a BET surface area of at least 3 m 2 / g, wherein in
  • LixNiaCObMn c Oz (I) the variables are defined as follows:
  • 0.4 ⁇ c ⁇ 0.65, preferably 0.4 ⁇ c ⁇ 0.6, 1, 1 ⁇ x ⁇ 1, 3, preferably 1, 12 ⁇ x ⁇ 1, 26, x + a + b + c - 0.2 ⁇ z ⁇ x + a + b + c + 0.2 a + b + c 1 where c / a is 1, 2, and wherein the material has a BET surface area of at least 3 m 2 / g.
  • the BET surface area can be determined, for example, by nitrogen adsorption, for example according to DIN ISO 9277: 2003-05.
  • materials according to the invention have a BET surface area of at most 15 m 2 / g.
  • materials according to the invention essentially have a layer structure, ie they are layer oxides.
  • the structure of the respective crystal lattice can be determined by methods known per se, for example X-ray diffraction or electron diffraction, in particular by X-ray powder diffractometry.
  • materials according to the invention may be doped with a total of up to 2% by weight of metal ions selected from cations of Na, K, Rb, Cs, alkaline earth, Ti, V, Cr, Fe, Cu, Ag, Zn, B, Al, Zr, Mo, W, Nb, Si, Ga and Ge, preferably up to one weight%.
  • materials according to the invention are not doped.
  • doping is understood to mean, in one or more steps, at least one compound which has one or more cations selected from cations of Na, K, Rb, Cs, alkaline earth, in one or more steps in the preparation of inventive materials.
  • material according to the invention has up to a maximum of 1% by weight of sulfate or carbonate. In another embodiment of the present invention, material according to the invention has no detectable levels of sulfate and / or carbonate.
  • compound of the general formula (I) is present as an amorphous powder. In another embodiment of the present invention, compound of the general formula (I) is present as a crystalline powder.
  • material according to the invention is in the form of particles having a mean diameter (number average) in the range of 10 nm to 200 ⁇ m, preferably 20 nm to 30 ⁇ m, measured by evaluation of images taken by electron microscopy.
  • material is present as substantially spherical, secondary agglomerates of primary particles.
  • the particle diameter (D50) of the secondary agglomerates of material according to the invention can be in the range from 2 to 50 ⁇ m, preferably in the range from 2 to 25 ⁇ m, particularly preferably in the range from 4 to 20 ⁇ m.
  • Particle diameter (D50) in the context of the present invention denotes the mean particle diameter (weight average), as can be determined, for example, by light scattering.
  • electrochemical cells made with compound of general formula (I) have a high discharge capacity when cycled between 2.0 V and 4.6 V against elemental lithium, the electrochemical cells in question having no or only a very small amount Show a decrease in the voltage during cycling.
  • the average discharge voltage is typically between 2.0 V and 4.6 V versus elemental lithium when cycling and greater than 3.6 V at current rates of 25 mA / g.
  • Another object of the present invention are electrodes, containing material according to the invention.
  • Inventive material can also be referred to as material (A) in the context of the present invention.
  • compounds of the general formula (I) are used in electrodes according to the invention as a composite with electrically conductive, carbonaceous material.
  • compound of the general formula (I) may be treated with electrically conductive carbonaceous material, for example coated.
  • Such composites are also the subject of the present invention.
  • Electrically conductive, carbonaceous material can be chosen, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the abovementioned substances.
  • electrically conductive, carbonaceous material may also be referred to as carbon (B) for short.
  • electrically conductive carbonaceous material is carbon black.
  • Carbon black may, for example, be chosen from lamp black, 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 oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • impurities for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • sulfur or iron-containing impurities in carbon black are possible.
  • electrically conductive, carbonaceous material is partially oxidized carbon black.
  • electrically conductive, carbonaceous material is carbon nanotubes.
  • Carbon nanotubes carbon nanotubes, in 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.
  • 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 For example, decompose nitrogen.
  • 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.
  • a decomposition catalyst for example Fe, Co or preferably Ni.
  • graphene is understood as meaning almost ideal or ideal two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers.
  • the weight ratio of the compound of the general formula (I) to the electrically conductive carbonaceous material in the electrodes according to the invention is in the range from 200: 1 to 5: 1, preferably 100: 1 to 10: 1.
  • Another aspect of the present invention is an electrode, in particular a cathode, comprising at least one compound of the general formula (I), at least one electrically conductive, carbonaceous material and at least one binder.
  • Compound of the general formula (I), at least one electrically conductive, carbonaceous material and at least one binder are connected to electrode material, which is also an object of the present invention.
  • Suitable binders are preferably selected from organic (co) polymers.
  • Suitable (co) polymers, ie homopolymers or copolymers can be selected, for example, from (co) polymers obtainable by anionic, catalytic or free-radical (co) polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers from ethylene, propylene, styrene, (meth) acrylonitrile and 1, 3-butadiene.
  • polypropylene is suitable, furthermore polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile.
  • 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.
  • 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 with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3. Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene.
  • Another preferred binder is polybutadiene.
  • Suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.
  • binders are selected from those (co) polymers which have an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol, preferably up to 500,000 g / mol.
  • Binders may be crosslinked or uncrosslinked (co) polymers.
  • binders are selected from halogenated (co) polymers, in particular from fluorinated (co) polymers.
  • Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which contain at least one (co) monomer in copolymerized form which has at least one halogen atom or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule.
  • Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkylvinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • 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.
  • electrically conductive, carbonaceous material made of graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the abovementioned substances is selected in electrodes according to the invention.
  • electrode material according to the invention contains:
  • (B) in the range of 1 to 25% by weight, preferably 2 to 20% by weight of electrically conductive, carbonaceous material,
  • the geometry of electrodes according to the invention can be chosen within wide limits. It is preferred to design electrodes according to the invention in thin layers, for example with a thickness in the range from 10 ⁇ m to 250 ⁇ m, preferably from 20 to 130 ⁇ m.
  • electrodes according to the invention comprise a foil, for example a metal foil, in particular an aluminum foil, or a polymer foil, for example a polyester foil, which may be untreated or siliconized.
  • Another object of the present invention is the use of electrode materials according to the invention or electrodes according to the invention in electrochemical cells.
  • Another object of the present invention is a process for the production of electrochemical cells using electrode material according to the invention or of electrodes according to the invention.
  • Another object of the present invention are electrochemical cells containing at least one electrode material according to the invention or at least one electrode according to the invention.
  • Electrochemical cells according to the invention definitely serve as cathodes in electrochemical cells according to the invention.
  • Electrochemical cells according to the invention contain a counterelectrode which is defined as an anode in the context of the present invention and which can be, for example, a carbon anode, in particular a graphite anode, a lithium anode, a silicon anode or a lithium titanate anode.
  • Electrochemical cells according to the invention may be, for example, batteries or accumulators.
  • Electrochemical cells according to the invention can comprise, in addition to the anode and the electrode according to the invention, further constituents, for example conductive salt, nonaqueous solvent, separator, current conductor, for example of a metal or an alloy, furthermore cable connections and housing.
  • further constituents for example conductive salt, nonaqueous solvent, separator, current conductor, for example of a metal or an alloy, furthermore cable connections and housing.
  • electrical cells according to the invention contain at least one non-aqueous solvent, which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or non-cyclic ethers, cyclic and non-cyclic acetals and cyclic or non-cyclic organic Carbonates.
  • non-aqueous solvent which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or non-cyclic ethers, cyclic and non-cyclic acetals and cyclic or non-cyclic organic Carbonates.
  • suitable 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.
  • suitable 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.
  • Inventive electrochemical cells also contain at least one conductive salt.
  • Suitable conductive salts are in particular lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, L1CIO4, LiAsFe, L1CF3SO3, LiC (CnF 2n + IS02) 3, lithium imides such as LiN (CnF 2 n + IS02) 2, where n is an integer ranging from 1 to 20, LiN (S02F) 2 , Li2SiF6, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + IS02) mXLi, wherein m is defined as follows:
  • Preferred conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
  • L1CIO4 and particularly preferred are LiPF6 and LiN (CFsSO2) 2.
  • 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.
  • 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 may be selected from inorganic particle filled PET webs.
  • Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are, for example, in the range from 80 to 750 nm.
  • separators are selected from glass fiber paper.
  • Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk.
  • a metal foil developed as a bag is used as the housing.
  • Inventive electrochemical cells provide a high voltage and are characterized by a high energy density and good stability.
  • electrochemical cells according to the invention have a high discharge capacity when cycled between 2.0 V and 4.6 V against elemental lithium, with the electrochemical cells according to the invention showing no or only a very slight decrease in the voltage during cycling.
  • the average discharge voltage when cycling between 2.0 V and 4.6 V versus elemental lithium and current rates of 25 mA / g should be greater than 3.6V.
  • Inventive electrochemical cells can be combined with each other, for example in series or in parallel. Series connection is preferred.
  • Another object of the present invention is the use of inventive electrochemical cells in devices, especially in mobile devices.
  • mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships.
  • Other examples of mobile devices are those that you move yourself, for example computers, especially laptops, telephones or electrical tools, for example in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • electrochemical cells in devices according to the invention offers the advantage of a longer running time before reloading. If one wanted to achieve the same running time with electrochemical cells with a lower energy density, then one would have to put up with a higher weight for electrochemical cells.
  • Another object of the present invention is a process for the preparation of
  • Electrodes characterized in that one
  • LixNiaCObMn c Oz (I) where the variables are defined as follows: 0.2 ⁇ a ⁇ 0.5,
  • the mixing can be done in one or more steps.
  • compound of the general formula (I), carbon (B) and binder (C) are mixed in one step, for example in a mill, in particular in a ball mill. Subsequently, the mixture thus obtained is applied in a thin layer to a support, for example a metal or plastic film (D). Before or during installation in an electrochemical cell, the carrier can be removed. In other variants you keep the carrier.
  • compound of the general formula (I), carbon (B) and binder (C) are mixed in several steps, for example in a mill, in particular in a ball mill. So you can, for example, first compound of the general formula (I) and carbon (B) mix together. Thereafter, it is mixed with binder (C). Subsequently, the mixture thus obtained is applied in a thin layer to a support, for example a metal or plastic film (D). Before or during installation in an electrochemical cell, the carrier can be removed. In other variants, the carrier is not removed.
  • compound of the general formula (I), carbon (B) and binder (C) in water or an organic solvent for example N-methylpyrrolidone or acetone
  • the suspension thus obtained is applied in a thin layer on a support, for example a metal or plastic film (D) and the solvent is then removed by a heat treatment.
  • the carrier Before or during installation in an electrochemical cell, the carrier can be removed. In other variants you do not remove the carrier.
  • Thin layers in the sense of the present invention may, for example, have a thickness in the range from 2 ⁇ m to 250 ⁇ m.
  • the electrodes can be treated thermally or preferably mechanically, for example by compression or calendering.
  • a carbonaceous conductive layer is formed by forming a mixture containing at least one compound of the general formula (I) and at least one carbonaceous thermally decomposable compound, and subjecting this mixture to thermal decomposition.
  • a carbon-containing conductive layer is formed by, during the synthesis of the compound of general formula (I) at least one carbon-containing thermally decomposable compound is present, which by decomposition forms a carbonaceous conductive layer on the compound of general formula (I).
  • the process according to the invention is well suited for the production of electrode material according to the invention and electrodes obtainable therefrom.
  • a further subject of the present invention are composites containing at least one compound of the general formula (I)
  • LixNiaCObMn c Oz (I) where the variables are defined as follows: 0.2 ⁇ a ⁇ 0.5,
  • compound of the general formula (I) has a BET surface area of at least 3 m 2 / g, and at least one electrically conductive, carbonaceous material, also called carbon (B).
  • compound of the general formula (I) is treated with carbon (B), for example coated.
  • compounds of general formula (I) and carbon (B) are present in composites of the invention in a weight ratio in the range of 98: 1 to 12: 5, preferably 48: 1 to 7: 2.
  • Composites according to the invention are especially suitable for the production of electrode material according to the invention. A method for their preparation is described above and also the subject of the present invention.
  • Another object of the present invention is a process for the preparation of compounds of the general formula (I) according to the invention, also called synthesis method according to the invention.
  • the synthesis process according to the invention can be carried out by first preparing a precursor, also called precursor, which is the transition metals in the desired ratio and optionally the doping (s), preferably by precipitation of mixed carbonates, which may be basic.
  • a precursor also called precursor
  • the mixture is first mixed with a lithium compound, preferably with lithium hydroxide or with L12CO3, and calcined.
  • the calcination is carried out at a maximum temperature in the range of 700 to 1000 ° C, preferably 800 to 950 ° C.
  • the calcination is carried out for a period in the range of 0.5 to 48 hours, preferably 2 to 8 hours at the maximum temperature.
  • Quantities of dissolved salts refer to kg solution.
  • the mass fraction of Ni, Co, Mn and Na was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
  • the mass fraction of CO3 2 " was determined by treatment with phosphoric acid and measurement of the resulting CO2 by IR spectroscopy
  • the mass fraction of SO4 2" was determined by means of ion chromatography.
  • Solution A An aqueous solution of transition metal salts was prepared by dissolving nickel sulfate, cobalt sulfate and manganese (II) sulfate in the molar ratio a: b: c.
  • the total transition metal concentration of aqueous solution of transition metal salts was 1.665 mol / kg.
  • transition metal carbonate hydroxide precursors having a composition of Ni: Co: Mn in the molar ratio a: b: c precipitated, and a suspension formed in the precipitation apparatus.
  • volume V was 1.6 liters.
  • the precipitated solid was filtered off and washed with water. The solid thus obtained was dried in a drying oven at 105 ° C for 16 hours and then sieved through a sieve with mesh size 50 ⁇ .
  • Table 1 Relative molar composition of the transition metals in the precursors P.1 to P.3 and V-P.4 to V-P.6
  • Precursor and is given in wt .-%, based on the total precursor concerned.
  • Solution A An aqueous solution of transition metal salts was prepared by dissolving nickel sulfate, cobalt sulfate and manganese (II) sulfate in the molar ratio a: b: c.
  • the total transition metal concentration of solution was 1.650 mol / kg.
  • the precipitated solid was filtered off and washed with water.
  • the solid thus obtained was dried in a drying oven at 105 ° C for 16 hours and then sieved through a sieve with mesh size 50 ⁇ .
  • Table 1 a Relative molar composition of the transition metals in the comparative precursor VP.7
  • c denotes the concentration of the relevant transition metal in the relevant precursor and is stated in% by weight, based on the total precursor concerned.
  • Table 2 Composition of materials (A.1) to (A.6) according to the invention and of comparison materials
  • Carbon (B.1) carbon black, BET surface area of 62 m 2 / g, commercially available as "Super P Li” from Timcal
  • Carbon (B.2) graphite, commercially available as "KS 6" from Timcal
  • Binder (C.1) copolymer of vinylidene fluoride and hexafluoropropene, as a powder, commercially available as Kynar Flex® 2801 from Arkema, Inc.
  • a 1 mol / l solution of LiPF6 in ethylene carbonate / dimethyl carbonate (1: 1 based on mass fractions) was used.
  • the anode consisted of a lithium foil which was separated from the cathode by a glass fiber paper separator.
  • the electrochemical cells of the invention were cycled between 4.6V and 2.0V at 25 ° C (charged / discharged).
  • the charging and discharging currents were set at 25 mA g of cathode material.
  • the materials EZ.1 to EZ.6 according to the invention each have high specific discharge capacities, expressed in terms of maintaining the capacity expressed from the 2nd to the 19th cycle.
  • the inventive materials EZ.1 to EZ.6 each have good capacity retention of over 98%.
  • the total voltage window of an electrochemical cell is typically in the range of 4.6V-2.0V.
  • a technical problem with the use of cathode materials in batteries may arise when the voltage range at which the capacitance is delivered is very low is and / or changes from cycle to cycle. This is measured by that the specific discharge capacity is determined, which is used below 3.4V. In addition, it was therefore determined how much the specific discharge capacity increases below 3.4 V from the 2nd to the 19th cycle.
  • EZ (V-3) to EZ (V-5) are, due to their low total capacity and in particular their low overall capacity maintenance of less than 95%, significantly worse than cathode materials suitable as EZ.1 to EZ.6.

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Abstract

L'invention concerne des matériaux de formule générale (I) LixNiaCobMncOz (I), où les variables sont définies comme suit : 0,2 ≤ a ≤ 0,5 ; 0,0 ≤ b ≤ 0,4 ; 0,4 ≤ c ≤ 0,65 ; 1,1 ≤ x ≤ 1,3 ; x + a + b + c-0, 2 ≤ z ≤ x + a + b + c + 0,2 ; et a + b + c = 1, avec c/a ≥ 1,2. Le matériau présente une surface BET au moins égale à 3 m2/g. L'invention concerne en outre la production des matériaux de l'invention, ainsi que leur utilisation.
PCT/EP2012/074976 2012-01-06 2012-12-10 Matériaux, production et utilisation desdits matériaux WO2013102533A1 (fr)

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Cited By (3)

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CN103715416A (zh) * 2013-12-30 2014-04-09 华南师范大学 用于高容量锂离子电池正极材料Li[Li0.201Ni0.133Co0.133Mn0.533]O2的制备方法
DE102014218144A1 (de) * 2014-09-10 2016-03-10 Bayerische Motoren Werke Aktiengesellschaft Lithium-Zelle
CN110364711A (zh) * 2019-07-08 2019-10-22 光鼎铷业(广州)集团有限公司 一种梯度铷掺杂的镍钴锰正极材料及其制备方法

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WO2011071094A1 (fr) * 2009-12-07 2011-06-16 住友化学株式会社 Méthode de production d'un oxyde métallique composite du lithium, oxyde métallique composite du lithium et pile secondaire à électrolyte non aqueux

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WO2011040383A1 (fr) * 2009-09-30 2011-04-07 戸田工業株式会社 Poudre de matériau actif pour électrodes positives, procédé pour sa production et batterie secondaire à électrolyte non aqueux
WO2011071094A1 (fr) * 2009-12-07 2011-06-16 住友化学株式会社 Méthode de production d'un oxyde métallique composite du lithium, oxyde métallique composite du lithium et pile secondaire à électrolyte non aqueux

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103715416A (zh) * 2013-12-30 2014-04-09 华南师范大学 用于高容量锂离子电池正极材料Li[Li0.201Ni0.133Co0.133Mn0.533]O2的制备方法
CN103715416B (zh) * 2013-12-30 2015-11-18 华南师范大学 用于高容量锂离子电池正极材料Li[Li0.201Ni0.133Co0.133Mn0.533]O2的制备方法
DE102014218144A1 (de) * 2014-09-10 2016-03-10 Bayerische Motoren Werke Aktiengesellschaft Lithium-Zelle
CN110364711A (zh) * 2019-07-08 2019-10-22 光鼎铷业(广州)集团有限公司 一种梯度铷掺杂的镍钴锰正极材料及其制备方法

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