Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
  • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
• • 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
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
  • H01M4/8673—Electrically conductive fillers
• • 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
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/023—Porous and characterised by the material
  • H01M8/0234—Carbonaceous material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/023—Porous and characterised by the material
  • H01M8/0241—Composites
  • H01M8/0243—Composites in the form of mixtures
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
  • H01M12/085—Zinc-halogen cells or batteries
• • 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
• • 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
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• Electrodes their manufacture and use
• the present invention relates to electrodes containing
• M 1 is selected from Mo, W, V, Nb and Sb
• M 2 is selected from Fe, Ag, Cu, Ni, Mn and lanthanides
• M 3 is selected from B, C, N, Al, Si, P and Sn
• M 4 is selected from Li, Na, K, Rb, Cs, NH 4 , Mg, Ca and Sr
• a is a number in the range of 1 to 3
• b is a number in the range of 0.1 to 10
• c is a number in the range of zero to one
• d is a number in the range of zero to one
• e is a number in Range of zero to 5
• f is a number in the range of 1 to 28, and wherein compound of general formula (I) has a BET surface area in the range of 1 to 300 m 2 / g.
• the present invention relates to the use of electrodes according to the invention in electrochemical cells, for example in metal-air batteries, for example in cadmium-air batteries, aluminum-air batteries or iron-air batteries and in particular in Zn-air batteries. Furthermore, the present invention relates to a method for producing electrochemical cells according to the invention and to a method for producing electrodes according to the invention.
• electrochemical cells for example in metal-air batteries, for example in cadmium-air batteries, aluminum-air batteries or iron-air batteries and in particular in Zn-air batteries.
• the present invention relates to a method for producing electrochemical cells according to the invention.
• alternatives to conventional electrochemical cells have been sought, in which charge transport is carried out by more or less hydrated protons and their maximum voltage is limited.
• the so-called lithium-ion batteries are mentioned, in which the charge transport is ensured by lithium ions in non-aqueous solvents.
• many such batteries are sensitive to air and moisture, which in the worst case can lead to auto-ignition of defective lithium-i
• metal-air batteries for example zinc-air batteries.
• metal for example zinc
• metal is oxidized with air-oxygen in the presence of an alkaline electrolyte to form an oxide or hydroxide.
• the released energy is used electrochemically.
• Such batteries can be recharged by reducing the metal ions formed during the discharge.
• GDE cathode gas diffusion electrodes
• Gas diffusion electrodes are porous and have a bifunctional effect.
• Metal-air batteries must allow the reduction of atmospheric oxygen to hydroxide ions during discharge and the oxidation of the hydroxide ions to oxygen during charging.
• the choice of the catalyst (s) is of great importance.
• pure discharge catalysts such as metal oxides such.
• metal oxides such as B. Mn0 2 , Co 3 0 4 , La 2 0 3 , LaNi0 3 , NiCo 2 0 4 , LaMn0 3 and LaNi0 3 , metals such as Ag, metal complexes such as CoTMMP (tetra methoxylphenyl-porphyrin) and FeTMMP-CI
• Metal nitrides such as Mn 4 N, CrN, Fe 2 N, metal carbides such as TaC, TiC and WC, and bifunctional catalysts, for example perovskites such as Lao, sSro, 2 B0 3 , see V. Neburchilov et al., J. Power Scources, 2010, 195, 1271, or La 0 , 6Ca 0 , 4 CoO 3 , see WO 2003/54989.
• WO 2007/065899 discloses bifunctional catalysts for secondary metal air batteries, in which the active layer of the electrode contains an oxygen reduction catalyst and a bifunctional catalyst selected from La 2 O 3 , Ag 2 O and spinels.
• an electrode material which consists of a baked mixture of graphite, NiS, FeW0 4 and WC, which is coated with cobalt. All the materials known from the prior art cited above can be further improved, which relates to at least one of the following properties: electrocatalytic activity, resistance to chemicals, electrochemical corrosion resistance, mechanical stability, good adhesion to the support material and little interaction with conductive black , Binder and - if present - Entladekatalysator.
• electrodes defined above also called electrodes according to the invention in the context of the present invention, contain
• (A) a solid medium through which gas can diffuse, in the context of the present invention also called medium (A) or carrier (A),
• M 1 is selected from Mo, W, V, Nb and Sb,
• M 2 is selected from Fe, Ag, Cu, Ni, Mn and lanthanides
• M 3 is selected from B, C, N, Al, Si, P and Sn,
• M 4 is selected from Li, Na, K, Rb, Cs, NH 4 , Mg, Ca and Sr, a is a number in the range of 1 to 3, b is a number in the range of 0.1 to 10, c is a number in the range of zero to one, d is a number in the range of zero to one, e is a number in the range of zero to 5, f is a number in the range of 1 to 28, and wherein compound of the general formula (I) has a BET surface area in the range of 1 to 300 m 2 / g.
• medium (A) As a solid medium through which gas can diffuse, also referred to as medium (A) for short, in the context of the present invention, preferably those porous bodies through which oxygen or air can diffuse without applying overpressure, for example metal nets and carbon gas diffusion media, in particular activated carbon, and carbon on a metal net.
• the gas permeability can be determined, for example, by the Gurley method in analogy to the measurement of the gas permeability of paper or paperboard.
• medium (A) has a porosity in the range of 20 to 1000 seconds for 10 cm 3 of air, preferably 40 to 120 seconds / 10 cm 3 . There are seconds for "seconds after Gurley".
• air or atmospheric oxygen may flow through the medium (A) substantially unimpeded.
• medium (A) is a medium which conducts electrical current.
• medium (A) is chemically indifferent to the reactions that take place in an electrochemical cell during normal operation, ie during charging and discharging.
• carbon medium (A) is selected which has a BET internal surface area in the range of from 20 to 1500 m 2 / g, which is preferably determined to be the apparent BET surface area.
• medium (A) is selected from metal nets, for example nickel nets or tantalum nets. Metal nets can be coarse or fine mesh.
• media (A) is selected from fabrics, mats, felts, or nonwovens containing metal filaments.
• gas diffusion media such as activated carbon, aluminum-doped zinc oxide, antimony-doped tin oxide or porous carbides or nitrides, such as WC, M02C, Mo 2 N, TiN, ZrN or TaC.
• Inventive electrodes furthermore contain at least one electrically conductive, carbonaceous material (B), also called conductive carbon (B) in the context of the present invention.
• Conductive carbon (B) can be selected, for example, from graphite, activated carbon, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
• conductive carbon (B) is carbon black.
• Carbon black may, for example, be selected 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.
• 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.
• medium (A) and conductive carbon (B) each as activated carbon
• medium (A) and conductive carbon (B) may be chemically different or preferably the same.
• Conductive carbon (B) may be present, for example, in particles having a diameter in the range of 0.1 to 100 mm, preferably 2 to 20 ⁇ m.
• conductive carbon (B) is partially oxidized carbon black.
• conductive carbon (B) is carbon nanotubes.
• Carbon nanotubes carbon nanotubes, in short CNT or English carbon nanotubes), for example single-walled carbon nanotubes (SW CNT) and preferably multi-walled carbon nanotubes (MW CNT), are known per se , A process for their preparation 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 of 0.4 to 50 nm, preferably 1 to 25 nm.
• carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
• Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
• Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
• Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
• Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
• the decomposition of volatile carbon-containing compounds or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
• 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.
• electrically conductive carbon (B) and in particular carbon black have a BET surface area in the range from 20 to 1500 m 2 / g, measured according to ISO 9277.
• Inventive electrodes contain at least one organic polymer, called polymer (C) or binder (C) for short.
• organic polymer also includes organic copolymers and denotes polymeric compounds in whose main chain mainly carbon atoms, ie at least 50 mol%, are to be found and which are obtained by free-radical polymerization, anionic, cationic or catalytic polymerization or can be prepared by polyaddition or polycondensation.
• Particularly suitable polymers (C) can be selected, for example, from (co) polymers obtainable by anionic, catalytic or free-radical (co) polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, polyethyleneimine 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.
• polymer (C) is polybutadiene.
• suitable polymers (C) are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.
• polymer (C) is 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.
• Polymers (C) may be crosslinked or uncrosslinked (co) polymers.
• polymers (C) are selected from halogenated (co) polymers, in particular from fluorinated ones
• Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which have 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, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, and ethylene - Chlorofluoroethylene copolymers.
• PVdF-HFP vinylidene fluoride-hexafluoropropylene copolymers
• PVdF-HFP vinylidene fluoride-tetrafluoroethylene copolymers
• perfluoroalkyl vinyl ether copolymers ethylene-t
• Suitable polymers (C) 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.
• Inventive electrodes furthermore contain at least one compound of the general formula (I) M aM 2 bM 3 cM 4 dH e Of (I) in particulate form, in short also called compound (D), where the variables are defined as follows: M 1 is selected from Mo, W, V, Nb and Sb, preferred are V, Mo and W, is selected from Fe, Ag, Cu, Ni, Mn and lanthanides, preferred are Fe, Ag and among the lanthanides La and Ce, M is 3 selected from B, C, N, Al, Si, P and Sn, preferred are P and Si,
• M 4 is selected from Li, Na, K, Rb, Cs, NH 4, Mg, Ca and Sr, NH are preferably 4, Li, K and Na, a is a number in the range of 1 to 3, preferably 1, b is a number in the range of 0.1 to 10, preferably 0.3 to 3, is a number in the range of zero to one, preferably to 0.2, is a number in the range of zero to one, preferably to 0.2 .
• compound of general formula (I) has a BET surface area in the range of 1 to 300 m 2 / g preferably from 1 to 100 m 2 / g, particularly preferably from 1 to 50 m 2 / g.
• variable f such that compound (D) is electrically neutral.
• variable f such that compound (D) is electrically non-neutral, for example, less than zero to -2. If one chooses variable e other than zero, the hydrogen is preferably present in hydroxide ions in compound (D).
• M 1 , M 2 , M 3 or M 4 are selected from mixtures of at least two elements.
• M 2 can be selected from mixtures of Fe and Ag.
• M 1 from mixtures of V and Mo.
• compound (D) is selected from mixed oxides and heteropolyacids and their salts, for example, ammonium or alkali metal salts. Preference is given to choosing compound (D) from mixed oxides.
• compound (D) is selected from Fe-Ag-X-O, Fe-V-X-O, Ag-V-X-O, Ce-X-O and Fe-X-O, where X is selected from tungsten and preferably molybdenum.
• the Fe-Ag-X-O is selected from compounds of the general formula (II)
• Fe-V-X-O is selected from compounds of the general formula (III)
• Ag-VX-0 is selected from compounds of the general formula (IV)
• Ce-X-O is selected from compounds of the general formula (V)
• Compound (D) is in particulate form.
• the particles may be regularly or irregularly shaped and have, for example, spherical shape, platelet shape, needle shape or irregular shape.
• compound (D) has an average primary particle diameter in the range of 10 to 50 nm.
• the mean primary particle diameter can be determined by microscopy, for example by
• compound (D) is present in the form of agglomerated particles, it being possible for the agglomerates to have an average diameter of 20 nm to 100 ⁇ m.
• agglomerates can look such that particles of compound (D) can be composed, for example, of at least two to several thousand primary particles.
• compound (D) has a BET surface area in the range of 1 to 300 m 2 / g, measured according to ISO 9277.
• compound (D) has a bimodal particle diameter distribution.
• electrodes according to the invention contain mixtures of at least two different compounds (D). In one embodiment of the present invention, electrodes according to the invention contain
• electrodes according to the invention further comprise at least one discharge catalyst (E).
• Entladekatalysatoren examples include La2Ü3, Ag2Ü, spinels such as LiM ⁇ C, ⁇ 2, Ag, CoTMMP (cobalt tetra [para- methoxyphenyl] porphyrin), FeTMMP-CI, Mn 4 N, CrN, Fe 2 N, TaC , TiC, WC, Co 3 0 4 , La 2Ü 3, LaNiO 3, N 1 CO 2 O 4, LaMnO-3, LaNiO 3, especially Ag and Ag / C.
• spinels such as LiM ⁇ C, ⁇ 2, Ag, CoTMMP (cobalt tetra [para- methoxyphenyl] porphyrin), FeTMMP-CI, Mn 4 N, CrN, Fe 2 N, TaC , TiC, WC, Co 3 0 4 , La 2Ü 3, LaNiO 3, N 1 CO 2 O 4, LaMnO-3, LaNiO 3, especially Ag and Ag / C.
• Discharge catalyst (E) is preferably in particulate form.
• the particles may be regularly or irregularly shaped and have, for example, spherical shape, platelet shape, needle shape or irregular shape.
• the average diameter of the particles of the discharge catalyst can be in the range from 2 nm to 100 ⁇ m.
• Particles of Ag also called Ag particles in the context of the present invention, may, for example, have an average diameter in the range from 2 to 200 nm, preferably 10 to 50 nm. If Ag is to be used as a discharge catalyst on carbon, the Ag particles can have a diameter in the range of 2 to 200 nm and the carbon particles have a diameter in the range of
• electrodes according to the invention comprise at least one discharge catalyst (E)
• electrodes according to the invention have in the range from 0.5 to 80% by weight of discharge catalyst (E), based on the sum of electrically conductive carbon (B), polymer (C) and compound (D).
• electrodes according to the invention contain Ag particles as discharge catalyst (E)
• electrodes according to the invention have in the range from 0.5 to 15% by weight, preferably from 2 to 6% by weight, of discharge catalyst (E) to the sum of electrically conductive carbon (B), polymer (C) and compound (D).
• electrodes according to the invention comprise Ag particles on carbon as discharge catalyst (E)
• electrodes according to the invention have in the range from 10 to 80% by weight, preferably 25 to 50% by weight, of discharge catalyst (E), based on the sum of electrically conductive carbon (B), polymer (C) and compound (D).
• electrodes according to the invention can have further components.
• suitable further components are solvents, which are understood as meaning organic solvents, in particular isopropanol, N-methylpyrrolidone, ⁇ , ⁇ -dimethylacetamide, amyl alcohol, n-propanol or cyclohexanone.
• Suitable solvents are organic carbonates, cyclic or non-cyclic, for example diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate, furthermore organic esters, cyclic or non-cyclic, for example methyl formate, ethyl acetate or ⁇ -butyrolactone (gamma-butyrolactone), and ethers, cyclic or non-cyclic, for example 1, 3-dioxolane.
• electrodes according to the invention may contain water.
• Inventive electrodes can be configured in various forms.
• the shape of electrodes according to the invention is essentially predetermined by the shape of the metal mesh.
• carrier (A) of activated carbon that in the case of finely divided activated carbon - for example, with an average particle diameter in the range of 0.1 to 100 ⁇ - the electrode as a formulation, for example as Paste or dough, applied to a metal mesh, a gas diffusion medium made of carbon or a carbon gas diffusion medium on a metal mesh.
• Another object of the present invention is the use of electrodes according to the invention in electrochemical cells, for example in non-rechargeable electrochemical cells, which are also called primary batteries, or in rechargeable electrochemical cells, which are also referred to as secondary batteries.
• Another object of the present invention is a process for the preparation of electrochemical cells using at least one electrode according to the invention.
• Another object of the present invention are electrochemical cells containing at least one electrode according to the invention.
• electrochemical cells according to the invention are Cd-air batteries, Fe-air batteries, AI-air batteries or zinc-air batteries.
• Electrochemical cells according to the invention may contain further constituents, for example a housing, which may have any shape, in particular the form of cylinders, disks or cuboids, furthermore at least one counterelectrode.
• the counterelectrode contains as essential constituent a metal in elemental form, for example Fe, Al, Cd or in particular zinc.
• the metal in elemental form may be formed as a solid plate, as a sintered, porous electrode or as a metal powder or granules, optionally sintered.
• the metal is in elemental form, in particular zinc, as a powder having an average particle diameter (number average) in the range of, for example 2 ⁇ to 500 ⁇ , preferably in the range of 30 to 100 ⁇ trained.
• the metal in the form of powder for improving the dimensional stability is added with an organic binder.
• organic binders are polysulfones, polyethersulfones and in particular fluorinated (co) polymers, for example polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF).
• the metal is used in the form of powder, especially zinc in the form of powder, as a paste or dough with an organic binder.
• Electrochemical cells according to the invention may further comprise at least one separator which mechanically separates the differently charged electrodes and thereby prevents a short circuit.
• Suitable separators are polymer films, in particular porous polymer films, which are unreactive towards metal in the elementary state and the usually strongly basic medium in electrochemical cells according to the invention.
• 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. In another embodiment of the present invention, separators can be selected from PET nonwovens filled with base-stable inorganic particles. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
• the electrode according to the invention for the production of electrochemical cells according to the invention, it is possible for example to proceed in such a way that the electrode according to the invention, the separator and the gene electrode combined with each other and optionally with other components in a housing.
• Electrochemical cells according to the invention may further comprise at least one electrolyte which is a combination of at least one solvent and at least one salt-like compound or a salt.
• suitable electrolytes are, in particular, aqueous bases, for example sodium hydroxide solution or potassium hydroxide solution.
• electrochemical cells according to the invention may contain a further electrode, for example as a reference electrode. Suitable as further electrodes are zinc wires, for example.
• Another object of the present invention is a process for the preparation of electrodes according to the invention, hereinafter also referred to as inventive production process.
• inventive production process For carrying out the preparation process according to the invention, it is possible, for example, to proceed in such a way that
• Compound (D) can be prepared, for example, by mixing suitable compounds of M 1 , of M 2 and optionally of M 3 and / or M 4 with one another, for example in dry form or as a solution or suspension.
• suitable compounds of M 1 , of M 2 and optionally of M 3 and / or M 4 with one another, for example in dry form or as a solution or suspension.
• the proportions of the compounds of M 1 , of M 2 and optionally of M 3 and / or M 4 in the stoichiometry of M 1 , M 2 , optionally M 3 and M 4 of compound (D) are selected.
• the mixture produced in this way is subsequently treated thermally, for example it may be calcined, for example calcined at temperatures in the range from 250 to 1000 ° C., preferably from 300 to 800 ° C.
• the calcination can be carried out under inert gas or under an oxidative atmosphere such as air (or other mixture of inert gas and oxygen).
• the duration of the calcination can be a few minutes to a few hours.
• Suitable starting materials for the preparation of compound (D) are oxides, hydroxides or oxohydroxides of M 1 , M 2 , M 3 and / or M 4 . Also suitable are those compounds of M 1 , M 2 , M 3 and / or M 4 , which react by heating in the presence or in the absence of oxygen to oxides, hydroxides or Oxohydroxiden.
• the mixing of the starting materials to prepare compound (D) may be carried out in dry or wet form. If it is desired to carry it out in dry form, the starting materials for the preparation of compound (D) can be used as finely divided powders and, after mixing and optionally compacting, subjected to calcination. Preferably, however, the intimate mixing takes place in wet form. Usually, the starting materials for the preparation of compound (D) in the form of aqueous solutions and / or suspensions will mix together.
• Particularly good mixtures of starting materials for the preparation of compound (D) can be obtained by starting only from present in dissolved compounds of M 1 , M 2 , M 3 and / or M 4 and compounds of M 1 , M 2 , M 3 and / or M 4 fails.
• the water-containing composition obtainable in this way is subsequently dried, preferably at temperatures in the range from 100 to 150.degree.
• Most notably preferred drying method is the spray drying, especially at outlet temperatures in the range of 100 to 150 ° C.
• steps can be taken to adjust the desired particle size of compound (D), for example, sieving, milling or classifying.
• compound (D) may be treated with electrically conductive carbon (B), for example by coating.
• electrically conductive carbon (B) for example by coating.
• mills for example, mills, in particular ball mills are suitable.
• carbon can be deposited on compound (D), for example by decomposition of organic compounds.
• polymer (C) which can be added, for example, in the form of an aqueous dispersion or granules.
• compound (D), electrically conductive carbon (B) and polymer (C), which can be added, for example, in the form of an aqueous dispersion or granules, are mixed in one step, for example by stirring the corresponding solids, if appropriate one or more organic solvents or with water.
• stirring apparatuses such as stirred tanks or mills, for example ball mills and in particular stirred ball mills.
• ultrasound is used, for example by means of a sonotrode.
• a preferably aqueous formulation is obtained.
• preferably aqueous formulation for example the viscosity or the solids content.
• ink preferably aqueous formulations which have a solids content in the range from 0.5 to 25%
• paste preferably aqueous formulations having a solids content above 25%
• the preferably aqueous formulation contains at least one surfactant.
• surfactants in the present Invention are surface-active substances.
• Surfactants can be selected from cationic, anionic and preferably nonionic surfactants.
• a medium (A) or a carrier (A) is provided, to which the preferably aqueous formulation or the preferably aqueous formulations, the electrically conductive carbon (B), polymer (C), compound (D) and optionally Entladekatalysator (E) contained, applied in one or more steps.
• the application can take place, for example, by compression, spraying, in particular with a spray gun, further knife-coating or preferably printing.
• a temperature in the range from 125 to 175.degree. C., preferably about 150.degree. C.
• vinylidene fluoride-hexafluoropropylene copolymers are chosen as the polymer (C).
• the temperature selected is 175 to 225, preferably about 200 ° C., and polyvinylidene fluoride as the polymer (C).
• the temperature chosen is 300 to 350.degree. C., preferably 320 to 325.degree. C., and polytetrafluoroethylene as polymer (C).
• An electrode according to the invention is obtained which can be combined with further constituents to form electrochemical cells according to the invention.
• a further aspect of the present invention are formulations, also called formulations according to the invention, containing at least one organic solvent or water and
• Aqueous formulations are preferred.
• aqueous formulations according to the invention comprise at least one further constituent selected from surfactants, thickeners and defoamers.
• aqueous formulations according to the invention may have a solids content in the range from 0.5 to 60%.
• a metal network was used as the support (A.1), which on one side had a (B.1) / (C.1 ) Mixture was coated. This coated metal mesh together with the coating was 400 ⁇ m thick and had an air permeability of 90 Gurleyseconds per 10 cm 3 .
• aqueous formulation WF.1 according to the invention was sprayed with a spray gun on a vacuum table which had a temperature of 75 ° C., nitrogen being used for spraying.
• a loading of 10 to 25 mg / cm 2 was calculated, calculated on the sum of (B.1), (C.1) and (D.1). It was then calendered with a calender, setting the calender as follows:
• the electrodes according to the invention showed a rest potential of 1.35 to 1.5 volts.
• the cell voltage dropped to 1, 2 to 1, 25 volts at a discharge current of 20 mA / cm 2 .
• the cell voltage increased to values between 1.95 and 2.00 V at a current density of 20 mA / cm 2 .
• the voltage during the discharge was 1, 1 to 1, 15 volts.
• voltages between 2.00 and 2.05 V were observed at a current density of 50 mA / cm 2 .
• the electrodes according to the invention achieved over 100 cycles in the electrochemical test cells (half cell).

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• 2011
  • 2011-06-17 EP EP11797704.1A patent/EP2586091A1/de not_active Withdrawn
  • 2011-06-17 CN CN2011800289266A patent/CN102948004A/zh active Pending
  • 2011-06-17 KR KR1020137001540A patent/KR20130036293A/ko not_active Application Discontinuation
  • 2011-06-17 WO PCT/IB2011/052645 patent/WO2011161598A1/de active Application Filing
  • 2011-06-17 JP JP2013516008A patent/JP2013535081A/ja not_active Withdrawn
  • 2011-06-21 TW TW100121692A patent/TW201228081A/zh unknown

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