EP2586093A1 - Electrodes, leur fabrication et leur utilisation - Google Patents

Electrodes, leur fabrication et leur utilisation

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Publication number
EP2586093A1
EP2586093A1 EP11797703.3A EP11797703A EP2586093A1 EP 2586093 A1 EP2586093 A1 EP 2586093A1 EP 11797703 A EP11797703 A EP 11797703A EP 2586093 A1 EP2586093 A1 EP 2586093A1
Authority
EP
European Patent Office
Prior art keywords
range
compound
lithium
present
zero
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11797703.3A
Other languages
German (de)
English (en)
Inventor
Arnd Garsuch
Alexander Panchenko
Andrey Karpov
Rüdiger Schmidt
Sabine Huber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11797703.3A priority Critical patent/EP2586093A1/fr
Publication of EP2586093A1 publication Critical patent/EP2586093A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8668—Binders
    • 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

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, 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 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 0.5, 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 lithium-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 lithium-air batteries.
  • 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.
  • 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.
  • electrochemical cells have a high energy density.
  • lithium-air batteries In a common embodiment, lithium is oxidized with atmospheric oxygen in a non-aqueous electrolyte to form an oxide or peroxide, that is, to form L12O or L12O2. The released energy is used electrochemically.
  • Such batteries can be recharged by reducing the metal ions formed during the discharge. It is known to use as a cathode gas diffusion electrodes (GDE). Gas diffusion electrodes are porous and have a bifunctional effect.
  • Metal-air batteries must allow the reduction of atmospheric oxygen to oxide or peroxide ions during discharge and the oxidation of oxide or peroxide ions to oxygen during charging. For example, it is known to build gas diffusion electrodes on a carrier material of finely divided carbon which has one or more catalysts for catalyzing the oxygen reduction or the evolution of oxygen.
  • 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 carbon black and binder.
  • 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), (B) at least one electrically conductive carbonaceous material,
  • 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 0.5, 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, carbon on metal mesh.
  • 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". In one embodiment of the present invention, 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.
  • medium (A) has a BET inner 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.
  • medium (A) is selected from electrically conductive fabrics, for example mats, felts or fleeces of carbon, containing metal filaments, for example tantalum filaments or nickel 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.
  • B electrically conductive, carbonaceous material
  • 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 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 oxygenated compounds. substance-containing groups such as 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, CNT or English carbon nanotubes
  • SW CNT single-walled carbon nanotubes
  • MW CNT multi-walled carbon nanotubes
  • carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
  • 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 especially carbon black have a BET surface area in the range of 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 refers to polymeric compounds in whose main chain mainly carbon atoms, ie at least 50 mol%, are to be found and which by free radical polymerization, anionic, cationic or catalytic lytic or Polyaddition or polycondensation can be produced.
  • 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. 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 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 (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, 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-tetra
  • 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.
  • polysulfones especially polyethersulfones.
  • Inventive electrodes furthermore contain at least one compound of the general formula (I)
  • M 1 is selected from Mo, W, V, Nb and Sb, preferred are V, Mo and W,
  • M 2 is selected from Fe, Ag, Cu, Ni, Mn and lanthanides, preferred are Fe, Ag and among the lanthanides La and Ce,
  • M 3 is 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, c is a number in the range of zero to one, preferably to 0.2, d is a number in the range of zero to one, preferably to 0 , 2, e is a number in the range of zero to 0.5, preferably to 0.1, 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, 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. In another embodiment of the present invention, one chooses variable f such that compound (D) is electrically non-neutral, for example, less than zero to -2.
  • 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-V-X-O 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 scanning electron microscopy or by transmission electron microscopy (TEM).
  • 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).
  • electrodes according to the invention contain
  • electrically conductive carbon (B) in the range from 20 to 80% by weight, preferably from 35 to 75% by weight, of electrically conductive carbon (B),
  • electrodes according to the invention may comprise further components.
  • Suitable further components are, for example, 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.
  • organic carbonates for example diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate
  • organic esters cyclic or non-cyclic, for example methyl formate, ethyl acetate or ⁇ -butyrolactone (gamma-butyrolactone)
  • 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 it is possible for the shape of electrodes according to the invention to be substantially predetermined by the shape of the metal grid.
  • carrier (A) of activated carbon that in the case of finely divided activated carbon - for example, with a mean particle diameter in the range of 0.1 to 100 ⁇ - the electrode as a formulation, for example as a paste, on a metal mesh, a carbon gas diffusion medium, 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 lithium-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 its essential constituent a metal in elemental form, for example pure lithium or a lithium alloy, for example lithium-tin alloy or lithium-silicon alloy or lithium-tin-silicon alloy.
  • 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 with respect to lithium in the elemental state and the electrolyte 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.
  • separators made of inorganic particles 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 of 80 to 750 nm.
  • glass fiber reinforced paper is also suitable.
  • electrochemical cells For the production of electrochemical cells according to the invention, it is possible, for example, to proceed by combining the electrode, separator and counterelectrode according to the invention with one another and, if appropriate, introducing further components into a housing.
  • Electrochemical cells according to the invention may further contain at least one electrolyte, which is a combination of at least one solvent and at least one salt-like compound or a salt.
  • 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.
  • polyalkylene glycols examples include 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 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 (VI) and (VI I)
  • 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 (VIII).
  • 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.
  • salts are in particular lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, LiCI0 4, LiAsF 6, LiCF 3 S0 3, LiC (C n F 2 n + IS02) 3, lithium imides such as LiN (C n F 2n + IS02) 2, where n is an integer Number in the range of 1 to 20 is 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 , LiCl 4 , and particularly preferred are LiPF 6 and LiN (CF 3 SO 2) 2.
  • suitable solvents are in particular propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and mixtures of at least two of the abovementioned solvents, in particular mixtures of ethylene carbonate with ethyl methyl carbonate or diethyl carbonate.
  • electrochemical cells according to the invention may contain a further electrode, for example as a reference electrode.
  • Suitable as further electrodes are, for example, lithium wires.
  • 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
  • the application can be done for example by spraying, for example spraying or spraying, further doctoring, printing or by pressing.
  • spraying is also counted by means of the application of a spray gun, a process which is frequently also referred to as "airbrushing” or “airbrushing” for short.
  • 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. preferential wise one chooses 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).
  • 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 are mixed 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.
  • Very particularly preferred drying method is spray drying, in particular 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.
  • aqueous formulation for example the viscosity or the solids content.
  • ink those preferably aqueous formulations which have a solids content in the range from 0.5 to 25% are referred to as ink.
  • paste Such preferably aqueous formulations having a solids content above 25% are referred to as paste.
  • the preferably aqueous formulation contains at least one surfactant.
  • Surfactants in the context of 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 preferably aqueous formulations containing electrically conductive carbon (B), polymer (C) and compound (D) are added, in one or more steps.
  • the application can be carried out, for example, by pressing, spraying, in particular with a spray gun, further knife-coating or preferably printing.
  • mixtures of the solvent-free components of electrically conductive carbon (B), polymer (C) and compound (D) can be pressed together, for example at pressures in the range from 30 to 300 bar and temperatures in the range from 150 to 320 ° C. You can do that starting from a paste, preferably from an aqueous paste whose layer height can be adjusted by means of shims by rolling and cutting and which is applied to the relevant medium (A).
  • 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).
  • thermal fixing steps are omitted.
  • An electrode according to the invention is obtained which can be combined with further constituents to form electrochemical cells according to the invention.
  • formulations also called formulations according to the invention, containing at least one organic solvent or water and
  • organic solvents are exemplified N-methylpyrrolidone, cyclohexanone and ⁇ , ⁇ -dimethylacetamide, preferably N-methylpyrrolidone.
  • 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%.
  • the mixture was mixed in a ball mill (Pulveristeette 6 from Fritsch): balls (diameter 10 mm,
  • the mixture was mixed in a ball mill (Pulveristeette 6 from Fritsch): balls (diameter 10 mm,
  • the substrate used was a glass fiber separator of the type 250 ⁇ GF / F from Whatman. Subsequently, ink WF1.1 according to the invention is sprayed with a spray gun on a vacuum table having a temperature of 75 ° C. using nitrogen for spraying. A catalyst loading of 5 mg / cm 2 was calculated, calculated on the sum (B.1), (C.1) and (D.1).
  • Example 11.1 was repeated, but with the ink WF1.2 according to the invention, and an electrode according to the invention was obtained.
  • Electrochemical cells according to FIG. 1 were built for the electrochemical characterization of the electrodes E 1 and E 2 according to the invention.
  • electrodes were used in addition to the invention:
  • Anode Li foil, 50 ⁇ thick,
  • Electrolyte 1 M LiPF6 in a 1: 1 mixture of ethylene carbonate / ethyl methyl carbonate.
  • Inventive electrochemical cell EZ.1 (based on inventive electrode Elektr.1) or electrochemical cell EZ.2 according to the invention (based on electrode 6 according to the invention) was obtained.
  • the electrodes according to the invention showed a rest potential of 3.0 to 3.2 volts. During discharge, the cell voltage dropped to 2.7 to 2.8 volts at a discharge current of 0.1 mA / cm 2 . During the charging process, the cell voltage increased to values between 3.6 and 4.4 V at a current density of 0.1 mA cm 2 .
  • the electrodes according to the invention achieved over 10 cycles in the electrochemical test cells (full cell).

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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
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Abstract

L'invention concerne des électrodes, contenant : (A) un milieu solide, à travers lequel du gaz peut se diffuser ; (B) au moins un matériau carboné électroconducteur ; (C) au moins un polymère organique ; (D) au moins un composé de formule générale (I) M1 aM2 bM3 cM4 dHeOf, sous forme de particules, les variables étant définies comme suit : M1 est choisie parmi Mo, W, V, Nb et Sb, M2 est choisie parmi Fe, Ag, Cu, Ni, Mn et les lanthanides, M3 est choisie parmi B, C, N, Al, Si, P et Sn, M4 est choisie parmi Li, Na, K, Rb, Cs, NH4, Mg, Ca et Sr, a est un nombre compris entre 1 et 3, b est un nombre compris entre 0,1 et 10, c est un nombre compris entre zéro et un, d est un nombre compris entre zéro et un, e est un nombre compris entre zéro et 0,5, f est un nombre compris entre 1 et 28, et le composé de formule générale (I) présentant une surface BET comprise entre 1 et 300 m2/g.
EP11797703.3A 2010-06-22 2011-06-17 Electrodes, leur fabrication et leur utilisation Withdrawn EP2586093A1 (fr)

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EP10166887 2010-06-22
PCT/IB2011/052642 WO2011161595A1 (fr) 2010-06-22 2011-06-17 Electrodes, leur fabrication et leur utilisation
EP11797703.3A EP2586093A1 (fr) 2010-06-22 2011-06-17 Electrodes, leur fabrication et leur utilisation

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JP (1) JP2013534697A (fr)
KR (1) KR20130093077A (fr)
CN (1) CN102948005A (fr)
CA (1) CA2801625A1 (fr)
TW (1) TW201222926A (fr)
WO (1) WO2011161595A1 (fr)

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TWI482660B (zh) * 2012-12-11 2015-05-01 Ind Tech Res Inst 電極及其製備方法
US10069075B2 (en) * 2013-02-26 2018-09-04 Nissan Chemical Industries, Ltd. Charge-transporting varnish
US9911981B1 (en) * 2014-04-10 2018-03-06 National Technology & Engineering Solutions Of Sandia, Llc Catalyzed, high energy density, metal-air battery
KR101674736B1 (ko) 2014-10-02 2016-11-10 한양대학교 산학협력단 리튬 공기 이차 전지, 및 그 제조 방법

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US4562124A (en) * 1985-01-22 1985-12-31 Westinghouse Electric Corp. Air electrode material for high temperature electrochemical cells
CN1324740C (zh) * 2005-08-19 2007-07-04 黑龙江大学 固体氧化物燃料电池阴极材料
JP5125461B2 (ja) * 2007-01-18 2013-01-23 株式会社豊田中央研究所 リチウム空気電池
CN101267057A (zh) * 2008-05-08 2008-09-17 复旦大学 高比能可充式全固态锂空气电池
CA2727266A1 (fr) * 2008-06-16 2010-01-14 Polyplus Battery Company Piles lithium/air aqueuses
JP4911155B2 (ja) * 2008-10-08 2012-04-04 トヨタ自動車株式会社 電池電極の製造方法
CN101533935A (zh) * 2009-04-14 2009-09-16 黄穗阳 高能安全可充式锂氧电池

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JP2013534697A (ja) 2013-09-05
CA2801625A1 (fr) 2011-12-29
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KR20130093077A (ko) 2013-08-21
TW201222926A (en) 2012-06-01
CN102948005A (zh) 2013-02-27

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