EP2548244A1 - Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques - Google Patents
Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiquesInfo
- Publication number
- EP2548244A1 EP2548244A1 EP11708504A EP11708504A EP2548244A1 EP 2548244 A1 EP2548244 A1 EP 2548244A1 EP 11708504 A EP11708504 A EP 11708504A EP 11708504 A EP11708504 A EP 11708504A EP 2548244 A1 EP2548244 A1 EP 2548244A1
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- European Patent Office
- Prior art keywords
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- general formula
- compound
- electrode material
- electrode
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Classifications
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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
- H01M4/58—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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/13—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
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/58—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
- H01M4/582—Halogenides
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 an electrode material comprising at least one compound of the general formula (I)
- M is at least one transition metal selected from Ti, Cr, V and Mn, wherein Ti, Cr, V and Mn may be partially substituted by Al, Ga, Ni, Fe or Co, a is a number in the range of 2.5 to 3.5
- b is a number in the range of 0.8 to 1, 2,
- c is a number in the range of 5.0 to 6.5 and
- d is a number in the range of zero to 1, 0.
- 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.
- Electrode materials defined above were found, which are also called electrode materials according to the invention in the context of the present invention.
- Inventive electrode materials contain at least one compound of the general formula (I)
- M is at least one transition metal selected from Ti, Cr, V and Mn, preferably Mn and V and particularly preferably V. Also mixtures of the above-mentioned transition metals are suitable, for example V / Mn mixtures or
- Ti, Cr, V or Mn may be partially substituted by Al, Ga, Ni, Fe or Co, for example in the range of 0.01 to 45 mol%, preferably up to 10 mol% and particularly preferably up to 2 mol%, based in each case on the total content of M.
- Preferred metals, by which may be substituted, are selected from Fe, Co and Ni.
- Ti, Cr, V and Mn are partially substituted by at least two of the metals Al, Ga, Ni, Fe or Co.
- proportions of less than 0.05 mol%, based on the total content of M are not considered as a substitution of M.
- Ti, Cr, V and Mn are not substituted by Al, Ga, Ni, Fe or Co, respectively.
- a is a number in the range of 2.5 to 3.5, preferably 2.8 to 3.2
- b is a number in the range of 0.8 to 1.2
- c is a number in the range of 5.0 to 6.5, preferably 5.8 to 6.2
- d is a number in the range of zero to 1.0, preferably to 0.3, more preferably zero.
- the formal oxidation state of M is +3.
- the mean oxidation state of M may be greater than +3. In another embodiment of the present invention, where d is zero, the average oxidation state of M is +3, and a corresponding number of sites in the crystal lattice remain vacant.
- Li is substituted up to 10 mol% by sodium, zinc or magnesium, for example in the range of 0.01 to 10 mol%, preferably 1 to 5 mol%.
- the oxidation state of M is +3, and a corresponding number of sites in the crystal lattice remain vacant.
- up to 10 mol% of Li is substituted by Na, Zn or Mg, and accordingly, in the case of substitution by Zn or Mg, F is substituted by oxygen.
- Li is neither substituted by sodium nor by zinc or magnesium.
- proportions of less than 0.05 mol%, based on the total content of Li are not regarded as substitution of Li.
- F is substituted in certain proportions by oxygen, that is, 0 ⁇ d ⁇ 1.0 without Li being substituted by Zn or Mg.
- the oxidation state of M may be greater than +3.
- Compound of the general formula (I) can be present in various modifications, for example as a-modification or as ⁇ -modification.
- the ⁇ -modification of compound of the general formula (I) has an orthorhombic crystal lattice. In general, the ⁇ -modification of compound of general formula (I) has a monoclinic crystal lattice.
- the structure of the respective crystal lattice can be determined by methods known per se, for example X-ray diffraction or electron diffraction.
- 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.
- compound of the general formula (I) is present 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 ,
- the compound of general formula (I) is present in electrode material according to the invention as a composite with electrically conductive, carbonaceous material.
- compound of the general formula (I) in electrode material according to the invention may be treated, for example coated, with electrically conductive, carbonaceous material.
- Such composites are also the subject of the present invention.
- Electrically conductive, carbonaceous material can be selected, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned 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 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 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.
- 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.
- graphene is understood as meaning almost ideal or ideally two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers.
- the weight ratio of the compound of the general formula (I) and the electrically conductive carbonaceous material is in the range of 200: 1 to 5: 1, preferably 100: 1 to 10: 1.
- Another aspect of the present invention is an electrode comprising at least one compound of the general formula (I), at least one electrically conductive, carbonaceous material and at least one binder.
- 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 selected 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 in copolymerized form and up to 50 mol% of at least one further comonomer, for example ⁇ -olefins such as propylene, butylene (cf.
- 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 in copolymerized form and up to 50 mol% of at least one further comonomer, for example ethylene and ⁇ -olefins, such as butylene.
- ethylene and ⁇ -olefins such as butylene.
- 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, carboxymethylcellulose, 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, perfluoroalkyl vinyl 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: in the range of 60 to 98% by weight, preferably 70 to 96% by weight, of compound of the general formula (I),
- binder in the range of 1 to 20% by weight, preferably 2 to 15% by weight of binder
- 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 of 10 ⁇ m to 250 ⁇ m, preferably 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 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.
- 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 may comprise further constituents in addition to the anode and the electrode according to the invention, 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.
- suitable polymers are in particular polyalkylene glycols, preferably poly-C 1 -C 4 -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, preferably 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 Acetaie 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) in which 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
- the solvent (s) are preferably used in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, determinable for example by Karl Fischer titration.
- Inventive electrochemical cells also contain at least one conductive salt. Suitable conductive salts are in particular lithium salts.
- lithium salts examples include LiPF 6, LiBF 4, LiCI0 4, LiAsF 6, LiCF 3 S0 3, LiC (C n F 2n + IS02) 3, lithium imides such as LiN (C n F 2n + IS02) 2, where n is an integer in Range is 1 to 20, LiN (SO 2 F) 2, Li 2 SiF 6, 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:
- Preferred conductive salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 , L1CIO 4 , and particularly preferred are LiPF 6 and LiN (CF 2 SO 2) 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 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. In another embodiment of the present invention, it is possible to choose separators made of PET particles filled with inorganic particles. 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.
- Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example a cuboid or the shape of a cylindrical disk. In one variant, 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.
- 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 electrochemical cells according to the invention in devices, in particular in mobile devices.
- mobile devices are vehicles, for example automobiles, two-wheelers, aircraft or watercraft, such as boats or ships.
- Other examples of mobile devices are those that you move yourself, such as computers, especially laptops, phones or electrical tools, for example, in the field of construction, in particular drills, cordless screwdrivers or battery tackers.
- electrochemical cells in devices according to the invention offer the advantage of a longer running time before reloading. If you wanted to use electrochemical If cells with lower energy densities realize a similar transit time, then one would have to accept a higher weight for electrochemical cells.
- Another object of the present invention is a process for the preparation of electrodes, characterized in that
- M is at least one transition metal selected from Ti, Cr, V and Mn, wherein Ti, Cr, V and Mn may be partially substituted by Al, Ga, Ni, Fe or Co, a is a number in the range of 2.5 to 3.5
- b is a number in the range of 0.8 to 1, 2,
- c is a number in the range of 5.0 to 6.5 and
- d is a number in the range of zero to 1, 0,
- 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 a Electrochemical cell can be removed from the carrier. In other variants you do not remove the carrier.
- compound of the general formula (I), carbon (B) and binder (C) in water or an organic solvent for example N-methylpyrrolidone or acetone
- 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. Before or during installation in an electrochemical cell see one can remove the carrier. 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 thermally or preferably mechanically treated, for example pressed or calendered.
- a carbon-containing conductive layer is formed by reacting a mixture containing at least one compound of the general formula ( I) and at least one carbon-containing, thermally decomposable compound is produced and this mixture is subjected to thermal decomposition.
- a carbonaceous conductive layer is formed by having at least one carbonaceous thermally decomposable compound present during the synthesis of the compound of general formula (I) which decomposes a carbonaceous conductive layer on the compound of general formula (I) Formula (I) forms.
- 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)
- LiaMbFcOd (I) where the variables are defined as follows: M is at least one transition metal selected from Ti, Cr, V and Mn, wherein Ti, Cr, V and Mn may be partially substituted by Al, Ga, Ni, Fe or Co, a is a number in the range of 2.5 to 3.5
- b is a number in the range of 0.8 to 1, 2,
- c is a number in the range of 5.0 to 6.5 and
- d is a number in the range of zero to 1, 0, 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 ranging from 98: 1 to 12: 5, preferably 48: 1 to 7: 2.
- Composites according to the invention are particularly 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 are compounds of general formula (I a), LiaMbFcOd " (I a) in which the variables are defined as follows:
- M is at least one transition metal selected from Ti, Cr, V and Mn, wherein Ti, Cr, V and Mn may be partially substituted by Al, Ga, Ni, Fe or Co, a is a number in the range of 2.5 to 3.5, preferably 2.8 to 3.2,
- b is a number in the range of 0.8 to 1, 2,
- c is a number in the range of 5.0 to 6.5, preferably 5.8 to 6.2 and zero ⁇ d * ⁇ 1.0, for example at least 0.1.
- Compounds of the invention are particularly suitable for the production of composites of the invention and for the production of electrode materials according to the invention.
- Another object of the present invention is a process for the preparation of compounds of general formula (I a) according to the invention, also called synthesis method according to the invention.
- the synthesis method according to the invention can be carried out so that one heats fluorides of lithium and of metal M with each other, wherein lithium fluoride and / or fluoride is not used as anhydrous fluorides, but as in moisture-containing environment, for example in the ambient air, stored fluorides, which may have physically adsorbed water ,
- Anhydrous fluorides such as LiF, OF3 and VF3 were dried under vacuum at 250 ° C and stored under dry argon to exclude moisture.
- Carbon (B.1) carbon black, BET surface area of 62 m 2 / g, commercially available as "Super P Li” from Timcal
- Binder (C.1) Polyvinylidene fluoride, as granules, commercially available as Solef® PVDF 1013 from Solvay. I. Preparation of compound of general formula I.
- Anhydrous LiF and anhydrous VF3 were mixed in a 3: 1 molar ratio and placed in an ampoule of copper or monel.
- the vial was sealed and kept in an oven under an inert gas atmosphere (nitrogen) at a temperature of 900 ° C for 14 hours. It was then cooled to room temperature. The heating and cooling rates were 3K / min.
- Anhydrous LiF and anhydrous VF 4 were mixed in a 3: 1 molar ratio and placed in an ampoule of copper or monel.
- the ampoule was sealed and kept in an oven under an inert gas atmosphere (nitrogen) at a temperature of 600 ° C for 14 hours. It was then cooled to room temperature. The heating and cooling rates were 3K / min. This gave ⁇ - (l.3) in the form of a powder.
- Anhydrous LiF and anhydrous OF3 were mixed in a molar ratio of 3: 1 and placed in an ampoule of copper or monel. The ampoule was sealed and placed in an oven under an inert gas atmosphere (nitrogen) for 14 hours at a
- compound of the general formula (I) was mixed with 15% by weight of carbon (B.1). This mixture was ground in a ball mill for 1 to 24 hours using stainless steel balls.
- a composite of the present invention was obtained from a compound of the general formula (I) and electrically conductive carbon in the form of a powder.
- Proportions of carbon black are based on proportion of compound of general formula (I)
- the entire electrode preparation described below was carried out in an intergas glove box with the exclusion of water and oxygen under argon as protective gas.
- 48 mg of the powder of a-Li3VF6 (orthorhombic crystal structure) from Example I.2 were mixed with 6 mg of carbon (B.1) and 6 mg (C.1) in an agate mortar and ground for about 10 minutes with a pestle.
- a cathode mixture was obtained.
- the way available electrodes were then stored for a period of 24 hours at 95 ° C in a vacuum oven. One received electrodes.
- the electrochemical characterization method used was a method called PITT (English: potentiostatic intermittent titration technique).
- PITT International: potentiostatic intermittent titration technique
- the voltage is not increased in fixed time steps, but the time per potential step is defined by a limiting current lum. If the current falls below lum, the potential is increased by ⁇ .
- this measuring principle allows, in contrast to cyclic voltammetry, a more accurate determination of the redox potentials of electrode processes with slow kinetics.
- the consideration of the amount of charge dq flowed per potential step shows by maxima the potentials at which the oxidation or reduction processes take place.
- the first charging and discharging process of two cells EZ.1 and EZ.2 according to the invention was investigated. The applied potential to lithium was varied between 3.0 V and 5.2 V, lum was set at 5.25 ⁇ .
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
L'invention concerne un matériau d'électrode qui contient au moins un composé de formule générale (I) LiaMbFcOd, dans laquelle les variables sont définies comme suit: M est au moins un métal de transition, sélectionné parmi Ti, Cr, V et Mn, Ti, Cr, V ou encore Mn pouvant être en partie substitués par Al, Ga, Ni, Fe ou Co; a est un nombre de l'ordre de 2,5 à 3,5; b est un nombre de l'ordre de 0,8 à 1,2; c est un nombre de l'ordre de 5,0 à 6,5 et d est un nombre de l'ordre de zéro à 1,0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11708504A EP2548244A1 (fr) | 2010-03-19 | 2011-03-18 | Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10157081 | 2010-03-19 | ||
EP11708504A EP2548244A1 (fr) | 2010-03-19 | 2011-03-18 | Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques |
PCT/EP2011/054097 WO2011113921A1 (fr) | 2010-03-19 | 2011-03-18 | Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2548244A1 true EP2548244A1 (fr) | 2013-01-23 |
Family
ID=44146985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11708504A Withdrawn EP2548244A1 (fr) | 2010-03-19 | 2011-03-18 | Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2548244A1 (fr) |
JP (1) | JP2013525941A (fr) |
KR (1) | KR20130040183A (fr) |
CN (1) | CN102893433A (fr) |
WO (1) | WO2011113921A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103959511A (zh) * | 2011-12-07 | 2014-07-30 | 巴斯夫欧洲公司 | 包含含氮聚合物的电化学电池 |
JP6046995B2 (ja) * | 2012-11-29 | 2016-12-21 | 日本電信電話株式会社 | ナトリウム二次電池の製造方法 |
CN105870452A (zh) * | 2016-05-19 | 2016-08-17 | 宁德新能源科技有限公司 | 一种正极材料,含有该正极材料的锂离子电池及制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009238687A (ja) * | 2008-03-28 | 2009-10-15 | Kyushu Univ | フッ化物電極活物質 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8658125B2 (en) | 2001-10-25 | 2014-02-25 | Panasonic Corporation | Positive electrode active material and non-aqueous electrolyte secondary battery containing the same |
JP2008234988A (ja) * | 2007-03-20 | 2008-10-02 | Sony Corp | 負極およびその製造方法、ならびに電池およびその製造方法 |
-
2011
- 2011-03-18 CN CN2011800243417A patent/CN102893433A/zh active Pending
- 2011-03-18 EP EP11708504A patent/EP2548244A1/fr not_active Withdrawn
- 2011-03-18 WO PCT/EP2011/054097 patent/WO2011113921A1/fr active Application Filing
- 2011-03-18 KR KR1020127026193A patent/KR20130040183A/ko not_active Application Discontinuation
- 2011-03-18 JP JP2012557561A patent/JP2013525941A/ja not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009238687A (ja) * | 2008-03-28 | 2009-10-15 | Kyushu Univ | フッ化物電極活物質 |
Non-Patent Citations (1)
Title |
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See also references of WO2011113921A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2011113921A1 (fr) | 2011-09-22 |
KR20130040183A (ko) | 2013-04-23 |
JP2013525941A (ja) | 2013-06-20 |
CN102893433A (zh) | 2013-01-23 |
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