WO1999019921A1 - MELANGES CONTENANT DES MATIERES SOLIDES RENFERMANT DU Li, APPROPRIES EN TANT QU'ELECTROLYTES SOLIDES OU SEPARATEURS POUR DES CELLULES ELECTROCHIMIQUES - Google Patents

MELANGES CONTENANT DES MATIERES SOLIDES RENFERMANT DU Li, APPROPRIES EN TANT QU'ELECTROLYTES SOLIDES OU SEPARATEURS POUR DES CELLULES ELECTROCHIMIQUES Download PDF

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Publication number
WO1999019921A1
WO1999019921A1 PCT/EP1998/005854 EP9805854W WO9919921A1 WO 1999019921 A1 WO1999019921 A1 WO 1999019921A1 EP 9805854 W EP9805854 W EP 9805854W WO 9919921 A1 WO9919921 A1 WO 9919921A1
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Prior art keywords
mixture
weight
ion
compound
conducting
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PCT/EP1998/005854
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German (de)
English (en)
Inventor
Stephan Bauer
Bernd Bronstert
Helmut MÖHWALD
Hans-Josef Sterzel
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Basf Aktiengesellschaft
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Priority to AU97438/98A priority Critical patent/AU9743898A/en
Publication of WO1999019921A1 publication Critical patent/WO1999019921A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • 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 mixtures which, inter alia, are suitable for electrochemical cells with lithium ion-containing electrolytes; their use e.g. in solid electrolytes, separators and electrodes; Solid electrolytes, separators. Electrodes, sensors, electrochromic windows, displays, capacitors and ion-conducting foils containing such a mixture; electrochemical cells with such solid electrolytes, separators and / or electrodes; and the use of the solids in the mixtures in electrochemical cells to improve the cycle stability.
  • Electrochemical, in particular rechargeable, cells are generally known, for example from “Ullmann's Encyclopedia of Industrial Chemistry", 5th ed. , Vol A3, VCH Verlagsgesellschaft mbH, Weinheim. 1985, pages 343-397.
  • the lithium batteries and the lithium ion batteries, in particular as secondary cells, occupy a special position due to their high specific energy storage density.
  • Such cells contain, in the cathode, as described, inter alia, in the above quotation from “Ullmann”, lithiated manganese, cobalt, vanadium or nickel mixed oxides, such as in the simplest stoichiometric case as LiMn 2 0 4 , LiCo0 2 , LiV 2 0 5 or LiNiO 2 can be described.
  • These compounds react reversibly with compounds that can incorporate lithium ions into their lattice, such as graphite, to expand the lithium ions from the crystal lattice, in which the metal ions such as manganese, cobalt or nickel ions are oxidized.
  • This reaction can be used in an electrochemical cell to store electricity by separating the compound which absorbs lithium ions, i.e. the anode material, and the mixed oxide containing lithium, i.e. the cathode material, by means of an electrolyte through which the lithium ions migrate from the mixed oxide into the anode material (charging process ).
  • the compounds suitable for the reversible storage of lithium ions are usually fixed on discharge electrodes by means of a binder.
  • an electrically insulating layer that is continuous for lithium cations between the two electrodes.
  • This can be a so-called solid electrolyte or an ordinary separator.
  • solid electrolytes and separators consist of a carrier material into which a dissociable compound containing lithium cations to increase the lithium ion conductivity and usually other additives such as solvents are incorporated.
  • US-A 5296318 and US-A 5429891 propose a copolymer of vinylidene difluoride and hexafluoropropene as the carrier material.
  • highly resistant (co) polymers has a number of disadvantages.
  • Such polymers are not only expensive, but are also difficult to dissolve. Furthermore, due to their comparatively low lithium cation conductivity, they increase the resistance of the cell, so that the electrolyte, which usually consists of a compound containing lithium cations, such as LiPF 6 , LiAsF 6 or LiSbF 6 and an organic solvent, is already in the manufacture of the insulating layer There is ethylene carbonate or propylene carbonate to add (US-A 5296318, US-A 5429891).
  • plasticizers for example di-n-butyl phthalate, and of pyrogenic silicas, which are added in order to ensure adequate filming and cohesion of the electrolyte layer and the ability to be bonded to the electrode layers and adequate conductivity and to ensure permeability to lithium cations.
  • the plasticizer must then be removed quantitatively from the layer composite of anode, solid electrolyte or separator layer and cathode layer by an extremely difficult and expensive extraction step before starting the batteries.
  • Solid electrolytes based on polyalkylene oxides are also known and are described, for example, in EP-A 559 317, EP-A 576 686, EP-A 537 930, EP-A 585 072 and US Pat. No. 5,279,910.
  • the polyethers described there have been modified at the end or functional groups, for example by (meth) acryloyl groups, and are crosslinked before use as a solid electrolyte by supplying energy (heat, light). They also generally contain a conductive salt, eg LiPF 6 , to improve their conductivity. speed.
  • a conductive salt eg LiPF 6
  • the object of the present invention is therefore to remedy the disadvantages mentioned and to provide a mixture which is particularly suitable for the production of solid electrolytes and separators, but is also used in the production of electrodes in electrochemical cells and for other applications described herein can be.
  • the use of the mixture according to the invention leads to solid electrolytes, separators or electrodes which, compared to the systems known hitherto, have an improved short-circuit strength, an increased pressure resistance, in particular at elevated temperatures above 120 ° C, as well as have a larger porosity, and are also able to sustainably suppress the formation of Li dendrites.
  • the presence of the solid also results in improved cycle stability and a higher current carrying capacity of an electrochemical cell.
  • the acid formed during the operation of an electrochemical cell is also trapped or neutralized.
  • the present invention relates to a mixture Ia comprising a mixture Ila consisting of a) 1 to 95% by weight of a Li-ion-conducting solid III, preferably a basic Li-ion-conducting solid III with a primary particle size of 5 nm to 20 ⁇ m and
  • weight fraction of the mixture Ila in the mixture la is 1 to 100% by weight.
  • the above mixture la is preferably a mixture comprising a mixture Ila consisting of a) 1 to 95 wt .-% of a Li-ion conductive solid III, preferably a basic Li-ion conductive solid III, with a primary particle size of 5 nm to 20 microns and
  • weight fraction of the mixture Ila in the mixture la is 1 to 100% by weight.
  • the present invention relates to a mixture Ib containing a mixture IIb consisting of a) 1 to 95% by weight of a Li-ion-conducting solid III, preferably a basic Li-ion-conducting solid III, with a primary particle size of 5 nm to 20 ⁇ m and
  • the solid III used is preferably inorganic Li-ion-conducting solids, more preferably an inorganic basic Li-ion-conducting solid, these solids preferably being selected from a Li-aluminate, a Li-aluminiosilicate, a Li-amide, a Li Borate, a Li carbonate, a Li carbide, a Li imide, a Li nitride, a Li oxide, a Li phosphate, a Li silicate, a Li sulfate, a Li zeolite and a mixture of two or more of them.
  • these solids preferably being selected from a Li-aluminate, a Li-aluminiosilicate, a Li-amide, a Li Borate, a Li carbonate, a Li carbide, a Li imide, a Li nitride, a Li oxide, a Li phosphate, a Li silicate, a Li sulfate, a Li ze
  • lithium borates such as Li 4 B 6 O n * xH 2 O, Li 3 (BO 2 ) 3 , Li 2 B 4 O 7 * xH 2 O, LiBO 2 , where x is a number from 0 to Can be 20; Lithium aluminates, such as Li 9 0 * A1 7 0 3 * H 9 0, Li, Al 9 O 4 , LiA10 2 ; Lithium aluminosilicates, such as, for example, lithium-containing zeolites, feldspar, feldspar representatives, phyllo and inosilicates, and in particular LiAl- Si 2 0 6 (spodumene), LiAlSi 4 O 10 (petullite), LiAlSi0 4 (eucryptite), mica, such as K [Li, Al] 3 [AlSi] 4 O 10 (F-OH) 2 JK [Li, Al, Fe] 3
  • Basic solids are particularly suitable.
  • Basic solids are to be understood to mean those whose mixture with a liquid, water-containing diluent, which itself has a pH of at most 7, has a higher pH than this diluent.
  • the solids should advantageously be largely insoluble in the liquid used as the electrolyte and be electrochemically inert in the battery medium.
  • Solids which have a primary particle size of 5 nm to 20 ⁇ m, preferably 0.01 to 10 ⁇ m and in particular 0.1 to 5 ⁇ m are particularly suitable, the specified particle sizes being determined by electron microscopy.
  • the melting point of the solids is preferably above the operating temperature customary for the electrochemical cell, melting points above 120 ° C., in particular above 150 ° C., having proven particularly favorable.
  • the solids can be symmetrical with respect to their outer shape, i.e. have a size ratio of height: width: length (aspect ratio) of approximately 1 and as spheres, granules, approximately round structures, but also in the form of any polyhedra, such as present as a cuboid, tetrahedron, hexahedron, octahedron or as a bipyramid, or be distorted or asymmetrical, i.e. have a size ratio of height: width: length (aspect ratio) of not equal to 1 and e.g.
  • the solids are in the form of asymmetrical particles, the upper limit for the primary particle size given above relates to the smallest axis in each case.
  • Compound VI is preferably selected from the group consisting of a mono- or polyhydric alcohol which has only carbon atoms in the main chain; a mono- or polyhydric alcohol which has at least one carbon atom in the main chain in addition to at least two Has an atom selected from the group consisting of oxygen, phosphorus and nitrogen; a silicon containing compound; an amine having at least one primary amino group: an amine having at least one secondary amino group; an amino alcohol; a mono- or polyvalent thiol; a compound having at least one thiol and at least one hydroxyl group; and a mixture of two or more of them.
  • compounds VI are preferred which have two or more functional groups which can react with the carboxylic acid or sulfonic acid.
  • monohydric or polyhydric alcohols which have only carbon atoms in the main chain, with 1 to 20, preferably 2 to 20 and in particular 2 to 10 alcoholic OH groups, in particular di-, tri- and tetravalent - Ge alcohols, preferably having 2 to 20 carbon atoms, such as ethylene glycol, propane-1, 2- or -1, 3-diol, butane-1, 2- or -1, 3-diol, butene-1, 4th - Butin-l, 4-diol, hexane-l, 6-diol, neopentyl glycol, dodecane-l, 2-diol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol A, but also, as from the above Definition is clear, monohydric alcohols, such as methanol, ethanol, propanol, n-, sec
  • Polyhydroxyolefins preferably those with two terminal hydroxyl groups, such as, for example, ⁇ , ⁇ -dihydroxybutadiene, can be used; Polyester polyols, as are known, for example, from Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, vol. 19, pp.
  • 62-65 and are obtained, for example, by reacting dihydric alcohols with polyhydric, preferably dihydric, polycarboxylic acids; monohydric or polyhydric alcohols which contain at least one oxygen atom in the main chain in addition to at least two carbon atoms, preferably polyether alcohols, such as, for example, polymerization products of alkylene epoxides, for example isobutylene oxide, propylene oxide, ethylene oxide, 1, 2-epoxybutane, 1, 2-epoxypentane, 1, 2 Epoxyhexane, tetrahydrofuran, styrene oxide, it also being possible to use polyether alcohols modified at the end groups, such as polyether alcohols modified with NH 9 end groups; these alcohols preferably have a molecular weight (number average) from 100 to 5000, more preferably 200 to 1000, and especially 300 to 800: such compounds are known per se and, for example, under the trademarks Pluriol ® or Pluronic ® (BA
  • Polyether diamines e.g. 4,7-dioxydecane-l, 10-diamine, 4, 1 1-dioxytetradecan-l, 14-diamine; a mono- or polyvalent thiol, e.g. aliphatic thiols, e.g.
  • aromatic thiols such as thiophenol, 4-chlorothiophenol, 2-mercaptoani
  • the compounds VI mentioned above are treated with a
  • Carboxylic acid or sulfonic acid VII which has at least one radically polymerizable functional group, or a derivative thereof or a A mixture of two or more of them is condensed, at least one, preferably all, of the free groups capable of condensation within the compounds VI being condensed with the compound VII.
  • carboxylic and sulfonic acids which have at least one free-radically polymerizable functional group and their derivatives can be used as carboxylic acid or sulfonic acid VII in the context of the present invention.
  • derivatives used here encompasses both compounds which are derived from a carboxylic or sulfonic acid which is modified on the acid function, such as e.g. Esters, acid halides or acid anhydrides, as well as compounds derived from a carbon or sulfonic acid modified on the carbon skeleton of the carbon or sulfonic acid, e.g. Halogen carbon or sulfonic acids.
  • compound VII ⁇ , ß-unsaturated carboxylic acids or / 3,7-unsaturated carboxylic acids.
  • ⁇ .ß-unsaturated carboxylic acids are those of the formula
  • R 1 , R 2 and R 3 represent hydrogen or C r to C 4 alkyl radicals, acrylic acid and methacrylic acid being preferred among these; cinnamic acid, maleic acid, fumaric acid, itaconic acid, or p-vinylbenzoic acid, and derivatives thereof, such as, for example, anhydrides, such as, for example, maleic or itaconic anhydride;
  • Halides in particular chlorides, such as, for example, acrylic or methacrylic acid chloride; Esters, such as (cyclo) alkyl (meth) acrylates with up to 20 carbon atoms in the alkyl radical, such as methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, stearyl, lauryl, Cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl (meth) acrylate, polypropylene glycol mono (meth) acrylates, polyethylene glycol mono (meth) acrylates, poly (meth) acrylates of polyhydric alcohols, such as, for example, glycerol di (meth) acrylate, trimethylol propane -di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, diethylene glycol bis
  • Vinyl esters of other aliphatic or aromatic carboxylic acids such as. B. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl stearate, vinyl palminate, vinyl crotonoate, divinyl adipate, divinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate; Allyl esters of other aliphatic or aromatic carboxylic acids, such as.
  • B vinyl acetic acid, 2-methyl vinyl acetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketene;
  • Sulfonic acids e.g. Vinylsulfonic acid, allyl and methallylsulfonic acid, and their esters and halides, vinyl benzenesulfonic acid ester, 4-vinylbenzenesulfonic acid amide.
  • Compounds X which can be used for free-radical polymerization and which can be used for the preparation of the polymer IX are as follows: olefinic hydrocarbons, such as ethylene, propylene, butylene. Isobutene, hexene or higher homologues and vinylcyclohexane; (Meth) acrylonitrile; halogen-containing olefinic compounds, such as vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene. 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoroethylene; Vinyl alcohol, vinyl acetate, N-vinyl pyrrolidone, N-vinyl imidazole, vinyl formamide;
  • Phosphorus nitride chlorides e.g. Phosphorus dichloride nitride, hexachlor (tri-phosphazene), and their derivatives which are partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, i.e. Compounds that can be polymerized to polyphosphazenes; aromatic, olefinic compounds such as e.g. Styrene, ⁇ -methylstyrene;
  • Vinyl ethers such as Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl vinyl ether.
  • These compounds X, as well as the condensation products V, are polymerized in a conventional manner, which is well known to the person skilled in the art, preferably free-radically polymerized, with regard to the molecular weights obtained what has been said hereinafter regarding compound VIII.
  • Compounds VIII are primarily compounds with an average molecular weight (number average) of at least 5,000, preferably 5,000 to 20,000,000, in particular 100,000 to 6,000,000, which are capable of solvating lithium cations and functioning as binders .
  • Suitable compounds VIII are, for example, polyethers and copolymers which have at least 30% by weight of the following structural unit, based on the total weight of compound VIII:
  • R 1 , R 2 , R 3 and R 4 represent aryl groups, alkyl groups, preferably methyl groups, or hydrogen, may be the same or different and may contain heteroatoms such as oxygen, nitrogen, sulfur or silicon.
  • Compound VIII can also consist of mixtures of two or more such compounds.
  • polymer mass IV or polymer IX defined above can also be in the form of a foam, in which case the solid II is present as such distributed therein.
  • the mixtures Ila should contain 1 to 95% by weight, preferably 25 to 90% by weight and in particular 30 to 70% by weight, of one Solids III and 5 to 99% by weight, preferably 10 to 75% by weight and in particular 30 to 70% by weight, consist of a polymeric mass IV, the compound VIII of the polymeric mass IV advantageously having an average molecular weight (number average) from 5,000 to 100,000,000, preferably 5 to 50,000 to 8,000,000.
  • the polymeric mass IV can be converted by reaction of 5 to 100% by weight, preferably 30 to 70% by weight, based on the polymeric mass IV of a compound V and 0 to 95% by weight, in particular 30 to 70% by weight. based on the polymeric mass IV of a compound VIII can be obtained.
  • the mixtures IIb should contain 1 to 95% by weight, preferably 25 to 90% by weight, and in particular 30 to 70% by weight, of a solid III and 5 to 99% by weight, preferably 10 to 75 %
  • By weight and in particular 30 to 70% by weight consist of a polymer IX, wherein compound VIII of polymer IX should advantageously have an average molecular weight (number average) of 5,000 to 100,000,000, preferably 50,000 to 8,000,000 .
  • the polymer IX can be converted by reaction of 5 to 75% by weight, preferably 30 to 70% by weight, based on the polymer IX of a compound X and 25 to 95% by weight, in particular 30 to 70%
  • mixtures la and Ib according to the invention or the mixtures Ila and Ilb are discussed together and referred to as “mixture according to the invention” or “mixture according to the invention”.
  • Mixture in amounts of 1 to 100% by weight, preferably 35 to 100
  • plasticizers preferably plasticizers containing polyethylene oxide or polypropylene oxide, plasticizers.
  • Aprotic solvents preferably those which solvate Li ions, such as, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylene carbonate, propylene carbonate; Oligoalkylene oxides, such as, for example, dibutyl ether, di-tert-butyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-tert.-butoxy-2-methoxyethane, 1-tert.
  • Li ions such as, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylene carbonate, propylene carbonate
  • the mixtures according to the invention can be dissolved or dispersed in an inorganic, preferably an organic liquid diluent, the mixture according to the invention preferably having a viscosity of 100 to 50,000 mPas, and then in a manner known per se, such as spray coating, pouring, dipping, Spin coating, roller coating, printing in high, low or flat printing or screen printing, can be applied to a carrier material. Further processing can be carried out as usual, e.g. by removing the diluent and curing the mixture.
  • Suitable organic diluents are aliphatic ethers, in particular tetrahydrofuran and dioxane, hydrocarbons, in particular hydrocarbon mixtures such as gasoline, toluene and xylene, aliphatic esters, in particular ethyl acetate and butyl acetate and ketones, in particular acetone, ethyl methyl ketone and cyclohexanone. Combinations of such diluents can also be used.
  • the materials usually used for electrodes come into consideration as carrier material.
  • Temporary intermediate carriers such as films, in particular polyester films, such as polyethylene terephthalate films, can also be used. Such films can advantageously be provided with a separating layer, preferably made of polysiloxanes.
  • the solid electrolytes and separators can also be produced thermoplastically, for example by injection molding, melt molding, pressing, kneading or extruding, if appropriate with a subsequent calendering step of the mixture according to the invention.
  • volatile components such as solvents or plasticizers, can be removed.
  • the mixture according to the invention can be crosslinked in a manner known per se, for example by irradiation with ionic or ionizing radiation, electron beam, preferably with an acceleration voltage between 20 and 2,000 kV and a radiation dose between 5 and 50 Mrad, UV or visible light, wherein in Usually, an initiator such as benzil dimethyl ketal or 1,3,5-trimethylbenzoyltriphenylphosphine oxide is advantageously added in amounts of in particular at most 1% by weight, based on the polymer composition IV or the polymer IX, and the crosslinking is generally within 0.5 up to 15 minutes can advantageously be carried out under inert gas such as nitrogen or argon; by thermal radical polymerization, preferably at temperatures above 60 ° C., an initiator such as azo-bis-isobutyronitrile being advantageously obtained in amounts of generally at most 5% by weight, preferably 0.05 to 1% by weight can add to the polymeric mass IV or the polymer IX; by electrochemically induced
  • the mixture according to the invention is to be used as a solid electrolyte or separator in an electrochemical cell, a dissociable compound containing lithium cations, a so-called conductive salt, and possibly further additives, such as in particular organic solvents, a so-called electrolyte, are incorporated.
  • Some or all of these substances can be added to the mixture during the production of the layer or introduced into the layer after the layer has been produced.
  • the generally known conductive salts can be used as conductive salts.
  • These conductive salts are used in amounts of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, in particular 1 to 10% by weight, based in each case on the mixture according to the invention.
  • Suitable organic electrolytes are the compounds discussed above under “plasticizers", preferably the customary organic see electrolytes, preferably esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate or mixtures of such compounds are used.
  • Solid electrolytes, separators and / or electrodes according to the invention suitable for electrochemical cells should advantageously have a thickness of 5 to 500 ⁇ m, preferably 10 to 500 ⁇ m, more preferably 10 to 200 ⁇ m and in particular 20 to 100 ⁇ m.
  • an electron-conducting, electrochemically active compound (cathode compound), preferably a lithium compound, conventionally used for cathodes is incorporated.
  • cathode compound preferably a lithium compound, conventionally used for cathodes.
  • anode material When used as an anode, a conventional electron-conducting electrochemically active compound (anode connection) known from the prior art is incorporated as anode material, the following in particular being mentioned: Lithium, lithium-containing metal alloys, micronized carbon black, natural and synthetic graphite, synthetically graphitized coal dust and carbon fibers, oxides such as titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, carbonates such as titanium carbonate, molybdenum carbonate, and zinc carbonate.
  • the mixture When used to produce or as an anode, up to 20% by weight, based on the total weight of the mixture, of conductive carbon black and, if appropriate, the customary additives mentioned above are added to the mixture according to the invention.
  • the mixture When used for the production of or as a cathode, the mixture contains, based on its total weight, 0.1 to 20% by weight of conductive carbon black.
  • the mixtures according to the invention can be used in electrochemical cells as the sole solid electrolyte and / or separator and / or electrode or in a mixture with other solid electrolytes, separators and / or electrodes.
  • the present invention relates to a composite body which can be used in particular in electrochemical cells, preferably in the form of a film, more preferably in the form of a film with a total thickness of 15 to 1500 ⁇ m, in particular with a total thickness of 50 to 500 ⁇ m, comprising at least a first layer, which contains an electron-conducting, electrochemically active compound, and at least one second layer, which contains the mixture according to the invention defined above and is free of an electron-conducting, electrochemically active compound.
  • the present invention further describes a method for producing such a composite body, which comprises the following steps:
  • the at least one second layer is preferably produced on a temporary carrier.
  • Temporary carriers usually used according to the invention such as e.g. a release film made of a polymer or a preferably coated paper, e.g. a siliconized polyester film can be used.
  • the production of this second layer is also on a permanent support, e.g. an arrester electrode or even completely without a carrier.
  • the layers defined above are brought together or produced by pressureless processes for coating or producing foils, such as Casting or knife coating, as well as by processing methods under pressure, e.g. Extruding, laminating, laminating, calendering or pressing. If necessary, the composite body produced in this way can be crosslinked or hardened by radiation, electrochemically or thermally.
  • the first layer defined above can also contain the mixture according to the invention.
  • an anode material for example tin oxide, conductive carbon black, the mixture according to the invention, a conductive salt and a plasticizer, for example propylene carbonate
  • a cathode material for example LiMn 2 O 4
  • a conductive electrode coated with conductive carbon black is placed on a conductive electrode coated with conductive carbon black and a mixture of the mixture according to the invention, a conductive salt and a plasticizer is poured onto it.
  • This composite is also subsequently irradiated with UV light (component 2).
  • a composite body anode / separator / cathode as described above can also be produced without the use of a carrier or the discharge electrodes, since the composite body obtained, consisting of a first and a second layer, as defined above, is in itself one for use in electrochemical cells has sufficient mechanical stability.
  • the filling of such composite bodies with an electrolyte and conductive salt can take place both before bringing the layers together, and preferably after the layers have been brought together, if necessary after contacting them with suitable discharge electrodes, for example a metal foil, and even after the composite body has been introduced into a battery housing, the special microporous structure of the layers when using the mixture according to the invention, in particular due to the presence of the solid defined above in the separator and possibly in the electrodes, the suction of the Electrolytes and the conductive salt and the displacement of the air in the pores. Filling can be carried out at temperatures from 0 ° C to approximately 100 ° C depending on the electrolyte used.
  • the electrochemical cells according to the invention can be used in particular as a car, device or flat battery.
  • the present invention also relates to the use of the mixture according to the invention or of the composite body described above for producing a solid electrolyte, a separator, an electrode, in a sensor, an electrochromic window, a display, a capacitor or an ion-conducting film, and a solid electrolyte, a separator, an electrode, a sensor, an electrochromic window, a display, a capacitor or an ion-conducting film, each of which contains the mixture according to the invention or the composite body described above.
  • an electrochemical cell comprising a solid electrolyte, separator or an electrode, as defined above, or a combination of two or more thereof, and the use of the electrochemical cell defined above as a car battery, device battery or flat battery.
  • the present invention relates generally to the use of a solid III with a primary particle size of 5 nm to 20 ⁇ m in a solid electrolyte, a separator or an electrode to increase the cycle stability of electrochemical cells, since it was found out when the present invention was completed has that the addition of such a solid has a very positive effect on this property of electrochemical cells.
  • the mixture was then applied to a siliconized release paper at 60 ° C. using a doctor blade with a casting gap of 300 ⁇ m, the diluent was removed within 5 minutes and, after the dried coating had been peeled off, an approximately 40 ⁇ m thick film was obtained, which was passed through 10 in an argon atmosphere minutes exposure at a distance of 5 cm under a field of superactin fluorescent tubes (TL 09, Philipps) was photocrosslinked.
  • the flexible film had excellent flexural strength. Bending radii well below 1 mm were tolerated without breaking.
  • the film showed no spherolite-like polyethylene oxide crystals and good swelling resistance in the organic electrolytes mentioned, which contain a conductive salt.
  • the organic electrolytes containing a conductive salt were absorbed in sufficient quantity by spontaneous diffusion within a few minutes with a swelling in weight of less than 50% by weight.
  • the swollen film had good strength.
  • the mixture was then applied to a siliconized release paper at 60 ° C. using a doctor blade with a casting gap of 750 ⁇ m, the thinner was removed within 5 minutes and, after the dried coating had been peeled off, an approximately 40 ⁇ m thick film was obtained, which was under an argon atmosphere was crosslinked by exposure for 10 minutes at a distance of 5 cm under a field of superactinic fluorescent tubes (TL 09, Philipps).
  • the flexible film had excellent flexural strength. Bending radii well below 1 mm were tolerated without breaking. Even after storage for more than two weeks at room temperature, the film showed no spherulite-like polyethylene oxide crystals and a satisfactory swelling resistance in the organic electrolytes mentioned, which contain a conductive salt.
  • the organic electrolytes containing a conductive salt were absorbed in sufficient quantity by spontaneous diffusion within a few minutes with a swelling in the weight of less than 150% by weight, with a considerable change in the size and thickness of the film.
  • the mixture was then applied to a siliconized release paper at 60 ° C. using a doctor blade with a casting gap of 300 ⁇ m, the diluent was removed within 5 minutes and an approximately 40 ⁇ m thick film was obtained after the dried coating had been peeled off.
  • the flexible film had excellent flexural strength. Bending radii well below 1 mm were tolerated without breaking.
  • the film After storage for more than two weeks at room temperature, the film showed small circular spherolite-like polyethylene oxide crystal zones and insufficient swelling resistance in the organic electrolytes mentioned, which contain a conductive salt. After just a few minutes of swelling, cracks appear or the film sticks together, so that the swollen film can no longer be handled.
  • Example 1 were added to a mixture of 30 g of a vinylidene fluoride-hexafluoropropene copolymers (Kynarflex ® 2822 company ELF-Atochem), 20 g of a silanized fumed silica (Aerosil R974, Degussa), whose aqueous suspension has a pH of 7, 50 g of dibutyl phthalate (Palatinol C, BASF Aktiengesellschaft) and 200 g of acetone 5% by weight, based on dibutyl phthalate, of trimethylolpropane trimethacrylate.
  • the mixture with a doctor blade with a gap of 750 microns was coated on a glass plate, immersed 15 minutes in a stream of air dried, and between 0.075 mm thick Mylar ® layers.
  • the 100 ⁇ m thick film layer was then crosslinked by irradiation with electrons having an energy of 4.5 MeV at a dose of 5 Mrad, with a dose of 2.5 Mrad being used per irradiation pass.
  • the flexible film had good flexural strength.
  • the plasticizer-free film showed good swelling resistance in the organic electrolytes containing a conductive salt.
  • the swollen film had good strength.

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Abstract

L'invention concerne un mélange (Ia) contenant un mélange (IIa) constitué de a) 1 à 95 % en poids d'une matière solide (III) conductrice pour les ions de Li, de préférence une matière solide basique (III), présentant une dimension de particules primaires comprise entre 5 nm et 20 νm, et b) 5 à 99 % en poids d'une matière polymère (IV) pouvant être obtenue par polymérisation de b1) 5 à 100 % en poids, par rapport à la matière (IV), d'un produit de condensation (V) et de b2) 0 à 95 % en poids par rapport à la matière (IV), d'un autre composé (VIII) présentant un poids moléculaire moyen (en nombre) d'au moins 5000 avec des segments polyéther dans la chaîne principale ou secondaire, le pourcentage en poids du mélange (IIa) par rapport au mélange (Ia) étant compris entre 1 et 100 % en poids.
PCT/EP1998/005854 1997-10-09 1998-09-15 MELANGES CONTENANT DES MATIERES SOLIDES RENFERMANT DU Li, APPROPRIES EN TANT QU'ELECTROLYTES SOLIDES OU SEPARATEURS POUR DES CELLULES ELECTROCHIMIQUES WO1999019921A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU97438/98A AU9743898A (en) 1997-10-09 1998-09-15 Mixtures with li-containing solids suitable as solid electrolytes or separators for electrochemical cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19744657 1997-10-09
DE19744657.4 1997-10-09

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WO1999019921A1 true WO1999019921A1 (fr) 1999-04-22

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AU (1) AU9743898A (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10216418A1 (de) * 2002-04-12 2003-10-30 Daramic Inc Batterieseparator mit verbesserter Oxidationsstabilität
EP1359637A1 (fr) * 2002-05-02 2003-11-05 VARTA Microbattery GmbH Procédé de fabrication d' un élément galvanique
DE102009016214A1 (de) * 2009-04-03 2010-10-14 Volkswagen Ag Verfahren zur Herstellung eines Teilchenverbundwerkstoffes sowie Verfahren zur Herstellung von Folien aus den Teilchenverbundwerkstoff und Bauteil, welches den Verbundwerkstoff umfasst
US10873106B2 (en) 2016-03-16 2020-12-22 University Of Utah Research Foundation Composite solid electrolytes for lithium batteries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3920129A1 (de) * 1988-06-21 1989-12-28 Ricoh Kk Elektrochemische vorrichtung
EP0557250A1 (fr) * 1992-01-17 1993-08-25 Enea Ente Per Le Nuove Tecnologie, L'energia E L'ambiente Electrolyte polymérique composite utilisable notamment dans les accumulateurs légers
WO1994024715A1 (fr) * 1993-04-08 1994-10-27 Shoshan, Herbert, Z. Electrolyte solide et piles
DE4431773A1 (de) * 1993-09-07 1995-03-09 Skc Ltd UV-härtbare Elektrolytzusammensetzung sowie Verfahren zu ihrer Herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3920129A1 (de) * 1988-06-21 1989-12-28 Ricoh Kk Elektrochemische vorrichtung
EP0557250A1 (fr) * 1992-01-17 1993-08-25 Enea Ente Per Le Nuove Tecnologie, L'energia E L'ambiente Electrolyte polymérique composite utilisable notamment dans les accumulateurs légers
WO1994024715A1 (fr) * 1993-04-08 1994-10-27 Shoshan, Herbert, Z. Electrolyte solide et piles
DE4431773A1 (de) * 1993-09-07 1995-03-09 Skc Ltd UV-härtbare Elektrolytzusammensetzung sowie Verfahren zu ihrer Herstellung

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10216418A1 (de) * 2002-04-12 2003-10-30 Daramic Inc Batterieseparator mit verbesserter Oxidationsstabilität
DE10216418B4 (de) * 2002-04-12 2006-02-09 Daramic, Inc. Batterieseparator, Verwendung eines Batterieseparators, Verfahren zur Herstellung eines Batterieseparators und Verwendung einer Verbindung
US9876209B2 (en) 2002-04-12 2018-01-23 Daramic, Inc. Battery separator with improved oxidation stability
US11018399B2 (en) 2002-04-12 2021-05-25 Daramic, Llc Battery separator with improved oxidation stability
EP1359637A1 (fr) * 2002-05-02 2003-11-05 VARTA Microbattery GmbH Procédé de fabrication d' un élément galvanique
US7141333B2 (en) 2002-05-02 2006-11-28 Varta Microbattery Gmbh Method for producing an electrochemical element
DE102009016214A1 (de) * 2009-04-03 2010-10-14 Volkswagen Ag Verfahren zur Herstellung eines Teilchenverbundwerkstoffes sowie Verfahren zur Herstellung von Folien aus den Teilchenverbundwerkstoff und Bauteil, welches den Verbundwerkstoff umfasst
US10873106B2 (en) 2016-03-16 2020-12-22 University Of Utah Research Foundation Composite solid electrolytes for lithium batteries

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AU9743898A (en) 1999-05-03
TW391073B (en) 2000-05-21

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