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EP2695222A2 - Electrochemical cells comprising ion exchangers - Google Patents

Electrochemical cells comprising ion exchangers

Info

Publication number
EP2695222A2
EP2695222A2 EP12767573.4A EP12767573A EP2695222A2 EP 2695222 A2 EP2695222 A2 EP 2695222A2 EP 12767573 A EP12767573 A EP 12767573A EP 2695222 A2 EP2695222 A2 EP 2695222A2
Authority
EP
European Patent Office
Prior art keywords
electrochemical cell
cell according
manganese
transition metal
lithium
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Withdrawn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
EP12767573.4A
Other languages
German (de)
French (fr)
Other versions
EP2695222A4 (en
Inventor
Klaus Leitner
Arnd Garsuch
Oliver Gronwald
Martin Schulz-Dobrick
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 EP12767573.4A priority Critical patent/EP2695222A4/en
Publication of EP2695222A2 publication Critical patent/EP2695222A2/en
Publication of EP2695222A4 publication Critical patent/EP2695222A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M50/44—Fibrous material
    • 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
    • H01M50/443—Particulate material
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • 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
    • H01M50/417—Polyolefins
    • 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
    • H01M50/431—Inorganic material
    • 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 electrochemical cells containing
  • At least one cathode comprising at least one lithium-ion-containing transition metal oxide which contains manganese as the transition metal
  • the present invention relates to the use of electrochemical cells according to the invention.
  • Electrochemical cells such as batteries or accumulators, can be used to store electrical energy.
  • batteries or accumulators can be used to store electrical energy.
  • lithium-ion batteries are superior in some technical aspects to conventional batteries. So you can create with them voltages that are not accessible with batteries based on aqueous electrolytes.
  • the materials from which the electrodes are made and in particular the material from which the cathode is made, play an important role.
  • lithium-containing transition metal mixed oxides in particular lithium-containing nickel-cobalt-manganese oxides having a layer structure, or manganese-containing spinels which may be doped with one or more transition metals.
  • a problem of many batteries remains the cycle stability, which is still to be improved.
  • Such batteries which contain a relatively high proportion of manganese, for example in the case of electrochemical cells with a manganese-containing spinel electrode and a graphite anode, it is frequently observed that there is a great loss of capacity within a relatively short time.
  • elemental manganese is deposited on the anode.
  • WO 2009/033627 discloses a sheet which can be used as a separator for lithium-ion batteries. It comprises a nonwoven as well as embedded in the nonwoven particles, which consist of organic polymers and which may be flattened by calendering. By means of such separators, it is possible to avoid short circuits which are formed by metal dendrites. In WO 2009/033627, however, no long-term cyclization experiments are disclosed. It was therefore the task to provide electrical cells that have an improved life and in which you must observe no deposition of elemental manganese even after several cycles. Accordingly, the electrochemical cells defined above were found.
  • cathode (A) at least one cathode, also called cathode (A) for short, containing at least one lithium-ion-containing transition metal oxide which contains manganese as the transition metal.
  • lithium ion-containing transition metal oxides are understood to mean not only those oxides which have at least one transition metal in cationic form, but also those which have at least two transition metal oxides in cationic form.
  • such compounds are also included under the term "lithium ion-containing transition metal oxides" which, in addition to lithium, comprise at least one metal in cationic form, which is not a transition metal, for example aluminum or calcium.
  • A) occur in the formal oxidation state + 4.
  • manganese occurs in cathode (A) in a formal oxidation state ranging from +3.5 to +4.
  • lithium ion-containing transition metal mixed oxide which contains less than 0.1% by weight of sodium is thus considered to be sodium-free in the context of the present invention. Accordingly, a lithium ion-containing transition metal mixed oxide containing less than 0.1 wt .-% sulfate ions, in the present invention as sulfate-free.
  • lithium ion-containing transition metal oxide is a transition metal mixed oxide containing at least one other transition metal in addition to manganese.
  • lithium ion-containing transition metal oxide is selected from manganese-containing lithium iron phosphates, and preferably from manganese-containing spinels and manganese-containing transition metal mixed oxides having a layer structure.
  • lithium-containing transition metal oxide is selected from those mixed oxides which have a greater than stoichiometric amount of lithium.
  • manganese-containing spinels are selected from those of the general formula (I)
  • M 1 is selected from one or more elements selected from Al, Mg, Ca, Na, B, Mo, W and transition metals of the first period of the Periodic Table of the Elements.
  • M 1 is selected from Ni, Co, Cr, Zn, Al, and most preferably M 1 is Ni.
  • manganese-containing spinels are selected from those of the formula LiNio.sMn-i.sC-d and LiM.sup.-C.
  • manganese-containing transition metal oxides having a layer structure of those of the formula (II) where the variables are defined as follows:
  • M 2 selected from Al, Mg, B, Mo, W, Na, Ca and transition metals of the first period of the Periodic Table of the Elements, wherein the or at least one transition metal is manganese.
  • At least 30 mol% of M 2 are selected from manganese, preferably at least 35 mol%, based on total content of M 2 .
  • M 2 is selected from combinations of Ni, Co and Mn which contain no other elements in significant amounts. In another embodiment, M 2 is selected from combinations of Ni, Co and Mn which contain at least one further element in significant amounts, for example in the range from 1 to 10 mol% of Al, Ca or Na.
  • manganese-containing transition metal oxides with a layered structure are selected from those in which M 2 is selected from Nio, 33Coo, 33Mno, 33, Ni 0 , 5Coo, 2Mn 0 , 3, Ni 0 , 4Coo, 3Mn 0 , 4, Ni 0 , 4Coo, 2Mn 0 , 4 and Ni 0 , 45Coo, ioMn 0 , 45.
  • lithium-containing transition metal oxide is in the form of primary particles agglomerated into spherical secondary particles, the average particle diameter (D50) of the primary particles being in the range of 50 nm to 2 ⁇ m, and the mean particle diameter (D50) of the secondary particles being in the range of 2 ⁇ to 50 ⁇ lies.
  • Cathode (A) may contain one or more other ingredients.
  • cathode (A) may contain carbon in conductive modification, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
  • cathode (A) may contain one or more binders, also called binders, for example one or more organic polymers.
  • Suitable binders are, for example, organic (co) polymers.
  • Suitable (co) polymers, ie homopolymers or copolymers can be selected, for example, from (co) polymers obtainable by anionic, catalytic or free-radical (co) polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers from ethylene, propylene, styrene, (meth) acrylonitrile and 1, 3-butadiene, in particular styrene-butadiene copolymers.
  • polypropylene is suitable, furthermore polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile.
  • polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene and up to 50 mol% of at least one further comonomer, for example ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • Polyethylene may be HDPE or LDPE.
  • polypropylene is understood to mean not only homo-polypropylene, but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene.
  • Polypropylene is preferably isotactic or substantially isotactic polypropylene.
  • polystyrene is understood to mean not only homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3 Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene.
  • Another preferred binder is polybutadiene.
  • Suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.
  • binders are selected from those (co) polymers which have an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol, preferably up to 500,000 g / mol. Binders may be crosslinked or uncrosslinked (co) polymers.
  • binders are selected from halogenated (co) polymers, in particular from fluorinated (co) polymers.
  • Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which contain at least one (co) monomer in copolymerized form which has at least one halogen atom or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule.
  • Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • Suitable binders are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
  • cathode (A) may comprise further conventional components, for example a current conductor, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil.
  • a current conductor which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil.
  • Aluminum foils are particularly suitable as metal foils.
  • cathode (A) has a thickness in the range of 25 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without Stromableiter.
  • Inventive electrochemical cells also contain at least one anode (B).
  • anode (B) may be selected from anodes of carbon and anodes containing Sn or Si.
  • carbon anodes may be selected from hard carbon, soft carbon, graphene, graphite, and especially graphite, intercalated graphite, and mixtures of two or more of the aforementioned carbons.
  • Anodes containing Sn or Si can be selected, for example, from nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composites and Si-metal or Sn metal alloys.
  • Anode (B) may comprise one or more binders. In this case, one can choose as binder one or more of the aforementioned binders.
  • anode (B) may have further conventional components, for example a current conductor, which may be designed in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a metal sheet.
  • a current conductor which may be designed in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a metal sheet.
  • metal foils in particular copper foils are suitable.
  • anode (B) has a thickness in the range of 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without Stromableiter.
  • (C) at least one layer, also called layer (C), containing
  • ion exchanger at least one ion exchanger in particulate form, also called ion exchanger (a) for short, and
  • ion exchangers (a) are known as such. In the context of the present invention, ion exchangers can have an average particle diameter in the range from 0.1 to 50 ⁇ m, preferably from 1 to 10 ⁇ m.
  • ionic exchangers in particulate form are selected from cationic synthetic resin ion exchangers (eg polystyrene resin or polyacrylate), the active group being an anionic group, for example sulfonic acid group or carboxylic acid group, furthermore consisting of molecular sieves, zeolites and lithium containing molecular sieves.
  • molecular sieves are preferably selected from natural and synthetic zeolites, which may be in the form of spheres (beads), powders or rods.
  • Preference is given to molecular sieve 4A, more preferably molecular sieve 3A.
  • Ion exchangers can be used as shaped articles, for example in the form of beads or rods, or as powders. Preference is given to moldings, in particular powders.
  • cationic ion exchangers are used.
  • ion exchangers are selected from at least partially lithiated ion exchangers or at least partially lithiated molecular sieves. At least partially lithiated ion exchangers or at least partially lithiated molecular sieves are understood to mean those cationic ion exchangers which largely replace H + and / or Na + or K + by Li + .
  • binder (b) is selected from such binders as described in connection with binder for the cathode (s) (A).
  • binder (b) is selected from polyvinyl alcohol, styrene-butadiene rubber, polyacrylonitrile, carboxymethyl cellulose and fluorine-containing (co) polymers.
  • binders (b) as well as binders for cathode and for anode, if present, are the same in each case.
  • binder (b) differs from binder for cathode (A) and / or binder for anode (B), or binder for anode (B) and binder for cathode (A) are different.
  • layer (C) serves as a separator.
  • a separator may contain, for example, a nonwoven which may be of inorganic or organic nature, or a porous plastic layer, for example a polyolefin membrane, in particular a polyethylene or a polypropylene membrane.
  • layer (C) then contains two porous plastic layers, between which ion exchanger (a) is embedded.
  • ion exchanger (a) is inserted in a layer of binder on the cathode (A) or on the anode (B), for example pressed in.
  • layer (C) may further include a nonwoven fabric (c).
  • Fleece (c) may be organic or preferably inorganic in nature.
  • organic nonwovens (c) are polyester nonwovens, in particular polyethylene terephthalate nonwovens (PET nonwovens), polybutylene terephthalate nonwovens (PBT nonwovens), polyimide nonwovens, polyethylene and polypropylene nonwovens, PVdF nonwovens and PTFE fleeces.
  • inorganic nonwovens (c) are glass fiber nonwovens and ceramic fiber nonwovens.
  • layer (C) has a thickness in the range from 0.1 ⁇ m to 250 ⁇ m, preferably 1 ⁇ m to 50 ⁇ m, and particularly preferably at least 9 ⁇ m.
  • Cells according to the invention may further comprise customary constituents, for example conductive salt, nonaqueous solvent, furthermore cable connections and housings.
  • 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 ethers and cyclic or non-cyclic organic Carbonates.
  • suitable polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
  • polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
  • the molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol
  • non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
  • 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 (X) and (XI)
  • 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 (XII).
  • the solvent or solvents are used in the so-called anhydrous state, i. with a water content in the range of 1 ppm to 0.1 wt .-%, determined for example by Karl Fischer titration.
  • Inventive electrochemical cells also contain at least one conductive salt.
  • Suitable conductive salts are in particular lithium salts.
  • suitable lithium salts are LiPF 6, LiBF 4, UCIO4, LiAsF 6, UCF3SO3, LiC (CnF 2n + IS02) 3, lithium imides such as LiN (CnF 2 n + IS02) 2, where n is an integer ranging from 1 to 20 , LiN (SO 2 F) 2, Li 2 SiFe, 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 conducting 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 2 SO 2) 2.
  • Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example cuboid or the shape of a cylinder. In another embodiment, electrochemical cells according to the invention have the shape of a prism. In one variant, a metal-plastic composite film prepared as a bag is used as the housing.
  • electrochemical cells provide a high voltage and are characterized by a high energy density and good stability.
  • electrochemical cells according to the invention are characterized by only a very small loss of capacity with prolonged use and repeated cycling.
  • Another object of the present invention is the use of electrochemical cells according to the invention in lithium-ion batteries.
  • Another object of the present invention are lithium-ion batteries, containing at least one electrochemical cell according to the invention.
  • Inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred.
  • Another object of the present invention is the use of inventive lithium-ion batteries in devices, especially in mobile devices.
  • mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships.
  • Other examples of mobile devices are those that you move yourself, for example computers, especially laptops, telephones or electrical tools, for example in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • lithium-ion batteries in devices according to the invention offers the advantage of a longer running time before recharging as well as a lower capacity loss with a longer running time. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells.
  • the lithiated molecular sieve (a.1) (LITHIUM SILIPORITE® G5000, Ceca) was dried for 16 hours at 200 ° C. in a vacuum oven. Thereafter, the thus dried lithiated Molsieb with mortar and pestle was crushed to a fine powder, which was seventh through a sieve with a mesh size of 32 ⁇ . The sieved fine powder was then mixed in a weight ratio of 9: 1 with polyvinylidene fluoride, commercially available as Kynar® FLEX 2801 from Arkema, (b.1), followed by dropwise addition of N-methylpyrrolidone until a viscous paste was obtained , The viscous paste thus obtained was stirred for a period of 16 hours.
  • polyvinylidene fluoride commercially available as Kynar® FLEX 2801 from Arkema, (b.1)
  • Example 1.1 The experiment of Example 1.1 was repeated under the same conditions, but the lithiated molecular sieve (a.1) was omitted. Comparative layer (V-C.3) was obtained.
  • Cathode (A.1) a lithium-nickel-manganese spinel electrode was used which was prepared as follows. One mixed with each other:
  • so-available paste was lazelte on 20 ⁇ thick aluminum foil and dried for 16 hours in a vacuum oven at 120 ° C. The thickness of the coating was 30 ⁇ after drying. Then punched out circular disk-shaped segments, diameter: 12 mm.
  • Anode (B.1) One mixed with each other
  • the so-available paste was lazelte on 20 ⁇ thick copper foil and dried for 16 hours in a vacuum oven at 120 ° C. The thickness of the coating was after drying 35 ⁇ . Then punched out circular disk-shaped segments, diameter: 12 mm.
  • the first two cycles were run at 0.2C rate for formation; Cycles # 3 through # 50 were cycled at 1 C rate.
  • the charging or discharging of the cell was carried out with the aid of a "MACCOR Battery Tester" at room temperature.
  • EZ. 1 and EZ.2 could be charged and discharged very well over 50 cycles.
  • the capacity hardly decreased (see Fig. 2 using the example of EZ.2). It could be shown that the battery capacity dropped from 7 mAh / g to 89 mAh / g after 50 cycles from initially 96 mAh / g, which corresponds to a capacity loss of 7.7%.
  • the charging / discharging efficiency reached values of over 99%.
  • Fig. 1 shows charge / discharge capacity (left axis, solid line) and charge / discharge efficiencies (right axis, dotted line) of the cell EZ.2 of the present invention

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Abstract

The present invention relates to electrochemical cells comprising (A) at least one cathode comprising at least one lithium ion-containing transition metal oxide comprising manganese as a transition metal, (B) at least one anode, and (C) at least one layer comprising (a) at least one ion exchanger in particulate form, (b) at least one binder.

Description

Elektrochemische Zellen, die Ionenaustauscher enthalten  Electrochemical cells containing ion exchangers
Die vorliegende Erfindung betrifft elektrochemische Zellen, enthaltend The present invention relates to electrochemical cells containing
(A) mindestens eine Kathode, enthaltend mindestens ein Lithiumionen-haltiges Übergangs- metalloxid, das als Übergangsmetall Mangan enthält,  (A) at least one cathode, comprising at least one lithium-ion-containing transition metal oxide which contains manganese as the transition metal,
(B) mindestens eine Anode, und  (B) at least one anode, and
(C) mindestens eine Schicht, enthaltend  (C) at least one layer containing
(a) mindestens einen Ionenaustauscher in partikulärer Form,  (a) at least one ion exchanger in particulate form,
(b) mindestens einen Binder.  (b) at least one binder.
Weiterhin betrifft die vorliegende Erfindung die Verwendung von erfindungsgemäßen elektrochemischen Zellen. Furthermore, the present invention relates to the use of electrochemical cells according to the invention.
Energie zu speichern ist schon seit langer Zeit ein Gegenstand wachsenden Interesses. Elek- trochemische Zellen, beispielsweise Batterien oder Akkumulatoren, können zur Speicherung von elektrischer Energie dienen. Besonderes Interesse genießen seit neuerer Zeit die sogenannten Lithium-Ionen-Batterien. Sie sind in einigen technischen Aspekten den herkömmlichen Batterien überlegen. So kann man mit ihnen Spannungen erzeugen, die mit Batterien auf der Grundlage von wässrigen Elektrolyten nicht zugänglich sind. Saving energy has been a subject of increasing interest for a long time. Electrochemical cells, such as batteries or accumulators, can be used to store electrical energy. Of particular interest since recently the so-called lithium-ion batteries. They are superior in some technical aspects to conventional batteries. So you can create with them voltages that are not accessible with batteries based on aqueous electrolytes.
Dabei spielen die Materialien, aus denen die Elektroden gemacht werden, und dabei insbesondere das Material, aus dem die Kathode gemacht wird, eine wichtige Rolle. In this case, the materials from which the electrodes are made, and in particular the material from which the cathode is made, play an important role.
In vielen Fällen verwendet man Lithium-haltige Übergangmetallmischoxide, insbesondere Li- thium-haltige Nickel-Kobalt-Mangan-Oxide mit Schichtstruktur, oder Mangan-haltige Spinelle, die mit einem oder mehreren Übergangsmetallen dotiert sein können. Ein Problem vieler Batterien bleibt jedoch die Zyklenbeständigkeit, die noch zu verbessern ist. Gerade bei solchen Batterien, die einen verhältnismäßig hohen Anteil an Mangan enthalten, beispielsweise bei elektrochemischen Zellen mit einer Mangan-haltigen Spinell-Elektrode und einer Graphit-Anode, be- obachtet man häufig einen starken Kapazitätsverlust innerhalb von relativ kurzer Zeit. Weiterhin kann man feststellen, dass in Fällen, in denen man als Gegenelektroden Graphitanoden wählt, elementares Mangan auf der Anode abgeschieden wird. In many cases, use is made of lithium-containing transition metal mixed oxides, in particular lithium-containing nickel-cobalt-manganese oxides having a layer structure, or manganese-containing spinels which may be doped with one or more transition metals. A problem of many batteries, however, remains the cycle stability, which is still to be improved. Especially in the case of such batteries, which contain a relatively high proportion of manganese, for example in the case of electrochemical cells with a manganese-containing spinel electrode and a graphite anode, it is frequently observed that there is a great loss of capacity within a relatively short time. Furthermore, it can be seen that in cases where one selects graphite anodes as counterelectrodes, elemental manganese is deposited on the anode.
WO 2009/033627 offenbart eine Lage, die als Separator für Lithium-Ionen-Batterien eingesetzt werden kann. Sie umfasst ein Vlies sowie in das Vlies eingelagerte Partikel, die aus organischen Polymeren bestehen und die durch Kalandrieren abgeplattet sein können. Durch derartige Separatoren kann man zwar Kurzschlüsse, die durch Metalldendriten gebildet werden, vermeiden. In WO 2009/033627 sind jedoch keine Langzeit-Zyklisierungs-Experimente offenbart. Es bestand also die Aufgabe, elektrische Zellen bereit zu stellen, die eine verbesserte Lebensdauer aufweisen und in denen man auch nach mehreren Zyklen keine Abscheidung von elementarem Mangan beobachten muss. Dem entsprechend wurden die eingangs definierten elektrochemischen Zellen gefunden. WO 2009/033627 discloses a sheet which can be used as a separator for lithium-ion batteries. It comprises a nonwoven as well as embedded in the nonwoven particles, which consist of organic polymers and which may be flattened by calendering. By means of such separators, it is possible to avoid short circuits which are formed by metal dendrites. In WO 2009/033627, however, no long-term cyclization experiments are disclosed. It was therefore the task to provide electrical cells that have an improved life and in which you must observe no deposition of elemental manganese even after several cycles. Accordingly, the electrochemical cells defined above were found.
Erfindungsgemäße elektrochemische Zellen enthalten Contain electrochemical cells according to the invention
(A) mindestens eine Kathode, kurz auch Kathode (A) genannt, enthaltend mindestens ein Lithiumionen-haltiges Übergangsmetalloxid, das als Übergangsmetall Mangan enthält.  (A) at least one cathode, also called cathode (A) for short, containing at least one lithium-ion-containing transition metal oxide which contains manganese as the transition metal.
Unter Lithiumionen-haltigen Übergangsmetalloxiden werden im Rahmen der vorliegenden Erfindung nicht nur solche Oxide verstanden, die mindestens ein Übergangsmetall in kationischer Form aufweisen, sondern auch solche, die mindestens zwei Übergangsmetalloxide in kationi- scher Form aufweisen. Außerdem werden im Rahmen der vorliegenden Erfindung auch solche Verbindungen unter dem Begriff„Lithiumionen-haltige Übergangsmetaloxide" mit umfasst, die neben Lithium - mindestens ein Metall in kationischer Form mit umfassen, das kein Übergangsmetall ist, beispielsweise Aluminium oder Calcium. Mangan kann in Kathode (A) in der formalen Oxidationsstufe +4 vorkommen. Bevorzugt kommt Mangan in Kathode (A) in einer formalen Oxidationsstufe im Bereich von +3,5 bis +4 vor. In the context of the present invention, lithium ion-containing transition metal oxides are understood to mean not only those oxides which have at least one transition metal in cationic form, but also those which have at least two transition metal oxides in cationic form. In addition, in the context of the present invention, such compounds are also included under the term "lithium ion-containing transition metal oxides" which, in addition to lithium, comprise at least one metal in cationic form, which is not a transition metal, for example aluminum or calcium. A) occur in the formal oxidation state + 4. Preferably, manganese occurs in cathode (A) in a formal oxidation state ranging from +3.5 to +4.
Viele Elemente sind ubiquitär. In gewissen sehrkleinen Anteilen sind beispielsweise Natrium, Kalium und Chlorid in praktisch allen anorganischen Materialien nachzuweisen. Im Rahmen der vorliegenden Erfindung werden Anteile von weniger als 0,1 Gew.-% von Kationen oder Anionen vernachlässigt. Ein Lithiumionen-haltiges Übergangsmetallmischoxid, welche weniger als 0,1 Gew.-% Natrium enthält, gilt im Rahmen der vorliegenden Erfindung also als Natrium-frei. Dementsprechend gilt ein Lithiumionen-haltiges Übergangsmetallmischoxid, die weniger als 0,1 Gew.-% Sulfationen enthält, im Rahmen der vorliegenden Erfindung als Sulfat-frei. Many elements are ubiquitous. In certain very small proportions, for example, sodium, potassium and chloride can be detected in virtually all inorganic materials. In the context of the present invention, proportions of less than 0.1% by weight of cations or anions are neglected. A lithium ion-containing transition metal mixed oxide which contains less than 0.1% by weight of sodium is thus considered to be sodium-free in the context of the present invention. Accordingly, a lithium ion-containing transition metal mixed oxide containing less than 0.1 wt .-% sulfate ions, in the present invention as sulfate-free.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Lithiumionen-haltigem Übergangsmetalloxid um ein Übergangsmetallmischoxid, das neben Mangan mindestens ein weiteres Übergangsmetall enthält. In einer Ausführungsform der vorliegenden Erfindung wählt man Lithiumionen-haltiges Übergangsmetalloxid aus Mangan-haltigen Lithium-Eisenphosphaten und bevorzugt aus Mangan- haltigen Spinellen und Mangan-haltigen Übergangsmetallmischoxiden mit Schichtstruktur. In one embodiment of the present invention, lithium ion-containing transition metal oxide is a transition metal mixed oxide containing at least one other transition metal in addition to manganese. In one embodiment of the present invention, lithium ion-containing transition metal oxide is selected from manganese-containing lithium iron phosphates, and preferably from manganese-containing spinels and manganese-containing transition metal mixed oxides having a layer structure.
In einer Ausführungsform der vorliegenden Erfindung wählt man Lithium-haltiges Übergangs- metalloxid aus solchen Mischoxiden, die einen überstöchiometrischen Anteil an Lithium aufweisen. In one embodiment of the present invention, lithium-containing transition metal oxide is selected from those mixed oxides which have a greater than stoichiometric amount of lithium.
In einer Ausführungsform der vorliegenden Erfindung wählt man Mangan-haltige Spinelle aus solchen der allgemeinen Formel (I) In one embodiment of the present invention, manganese-containing spinels are selected from those of the general formula (I)
LiaM1bMn3-a-b04-d (I) wobei die Variablen wie folgt definiert sind: Li a M 1 b Mn 3 -a-b04-d (I) where the variables are defined as follows:
0,9 < a < 1 ,3, bevorzugt 0,95 < a < 1 ,15, 0.9 <a <1, 3, preferably 0.95 <a <1, 15,
0 < b < 0,6, beispielsweise 0,0 oder 0,5, 0 <b <0.6, for example 0.0 or 0.5,
wobei für den Fall, dass man M1 = Ni wählt, bevorzugt gilt: 0,4 < b < 0,55, where, in the case of choosing M 1 = Ni, it is preferred that 0.4 <b <0.55,
-0,1 < d < 0,4, bevorzugt 0 < d < 0,1 , M1 wird gewählt aus einem oder mehreren Elementen, gewählt aus AI, Mg, Ca, Na, B, Mo, W und Übergangsmetallen der ersten Periode des Periodensystems der Elemente. Bevorzugt ist M1 gewählt aus Ni, Co, Cr, Zn, AI und ganz besonders bevorzugt ist M1 Ni. -0.1 <d <0.4, preferably 0 <d <0.1, M 1 is selected from one or more elements selected from Al, Mg, Ca, Na, B, Mo, W and transition metals of the first period of the Periodic Table of the Elements. Preferably, M 1 is selected from Ni, Co, Cr, Zn, Al, and most preferably M 1 is Ni.
In einer Ausführungsform der vorliegenden Erfindung wählt man Mangan-haltige Spinelle aus solchen der Formel LiNio.sMn-i.sC -d und LiM^C . In one embodiment of the present invention, manganese-containing spinels are selected from those of the formula LiNio.sMn-i.sC-d and LiM.sup.-C.
In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Mangan-haltige Übergangsmetalloxide mit Schichtstruktur aus solchen der Formel (I I) wobei die Variablen wie folgt definiert sind: In another embodiment of the present invention, manganese-containing transition metal oxides having a layer structure of those of the formula (II) where the variables are defined as follows:
0 < t < 0,3 und 0 <t <0.3 and
M2 gewählt aus AI, Mg, B, Mo, W, Na, Ca und Übergangsmetallen der ersten Periode des Periodensystems der Elemente, wobei das oder mindestens ein Übergangsmetall Mangan ist. M 2 selected from Al, Mg, B, Mo, W, Na, Ca and transition metals of the first period of the Periodic Table of the Elements, wherein the or at least one transition metal is manganese.
In einer Ausführungsform der vorliegenden Erfindung sind mindestens 30 mol-% von M2 ge- wählt aus Mangan, bevorzugt mindestens 35 mol-%, bezogen auf gesamten Gehalt an M2. In one embodiment of the present invention, at least 30 mol% of M 2 are selected from manganese, preferably at least 35 mol%, based on total content of M 2 .
In einer Ausführungsform der vorliegenden Erfindung ist M2 gewählt aus Kombinationen von Ni, Co und Mn, die keine weiteren Elemente in signifikanten Mengen enthalten. In einer anderen Ausführungsform ist M2 gewählt aus Kombinationen von Ni, Co und Mn, die mindestens ein weiteres Element in signifikanten Mengen enthalten, beispielsweise im Bereich von 1 bis 10 mol-% AI, Ca oder Na. In one embodiment of the present invention, M 2 is selected from combinations of Ni, Co and Mn which contain no other elements in significant amounts. In another embodiment, M 2 is selected from combinations of Ni, Co and Mn which contain at least one further element in significant amounts, for example in the range from 1 to 10 mol% of Al, Ca or Na.
In einer Ausführungsform der vorliegenden Erfindung wählt man Mangan-haltige Übergangsme- talloxide mit Schichtstruktur aus solchen, in denen M2 gewählt ist aus Nio,33Coo,33Mno,33, Ni0,5Coo,2Mn0,3, Ni0,4Coo,3Mn0,4, Ni0,4Coo,2Mn0,4 und Ni0,45Coo,ioMn0,45. In einer Ausführungsform liegt Lithium-haltiges Übergangsmetalloxid in Form von Primärpartikeln vor, die zu sphärischen Sekundärpartikeln agglomeriert sind, wobei der mittlere Partikeldurchmesser (D50) der Primärpartikel im Bereich von 50 nm bis 2 μηη und der mittlere Partikeldurchmesser (D50) der Sekundärpartikel im Bereich von 2 μηη bis 50 μηη liegt. In one embodiment of the present invention, manganese-containing transition metal oxides with a layered structure are selected from those in which M 2 is selected from Nio, 33Coo, 33Mno, 33, Ni 0 , 5Coo, 2Mn 0 , 3, Ni 0 , 4Coo, 3Mn 0 , 4, Ni 0 , 4Coo, 2Mn 0 , 4 and Ni 0 , 45Coo, ioMn 0 , 45. In one embodiment, lithium-containing transition metal oxide is in the form of primary particles agglomerated into spherical secondary particles, the average particle diameter (D50) of the primary particles being in the range of 50 nm to 2 μm, and the mean particle diameter (D50) of the secondary particles being in the range of 2 μηη to 50 μηη lies.
Kathode (A) kann einen oder mehrere weitere Bestandteile enthalten. Beispielsweise kann Kathode (A) Kohlenstoff in leitfähiger Modifikation enthalten, beispielsweise aus Graphit, Ruß, Kohlenstoffnanoröhren, Graphen oder Mischungen von mindestens zwei der vorstehend genannten Stoffen gewählt. Cathode (A) may contain one or more other ingredients. For example, cathode (A) may contain carbon in conductive modification, for example selected from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances.
Weiterhin kann Kathode (A) einen oder mehrere Binder, auch Bindemittel genannt, enthalten, beispielsweise ein oder mehrere organische Polymere. Geeignete Bindemittel sind beispielsweise organischen (Co)polymeren. Geeignete (Co)polymere, also Homopolymere oder Copolymere, kann man beispielsweise wählen aus durch anionische, katalytische oder radikalische (Co)polymerisation erhältlichen (Co)polymeren, insbesondere aus Polyethylen, Polyacrylnitril, Polybutadien, Polystyrol, und Copolymeren von mindestens zwei Comonomeren, gewählt aus Ethylen, Propylen, Styrol, (Meth)acrylnitril und 1 ,3-Butadien, insbesondere Styrol-Butadien- Copolymere. Außerdem ist Polypropylen geeignet, weiterhin sind Polyisopren und Polyacrylate geeignet. Besonders bevorzugt ist Polyacrylnitril. Furthermore, cathode (A) may contain one or more binders, also called binders, for example one or more organic polymers. Suitable binders are, for example, organic (co) polymers. Suitable (co) polymers, ie homopolymers or copolymers, can be selected, for example, from (co) polymers obtainable by anionic, catalytic or free-radical (co) polymerization, in particular from polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers from ethylene, propylene, styrene, (meth) acrylonitrile and 1, 3-butadiene, in particular styrene-butadiene copolymers. In addition, polypropylene is suitable, furthermore polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile.
Unter Polyacrylnitril werden im Rahmen der vorliegenden Erfindung nicht nur Polyacrylnitril- Homopolymere verstanden, sondern auch Copolymere von Acrylnitril mit 1 ,3-Butadien oder Styrol. Bevorzugt sind Polyacrylnitril-Homopolymere. Im Rahmen der vorliegenden Erfindung wird unter Polyethylen nicht nur Homo-Polyethylen verstanden, sondern auch Copolymere des Ethylens, die mindestens 50 mol-% Ethylen einpolyme- risiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispielsweise a-Olefine wie Propylen, Butylen (1-Buten), 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen, 1 - Penten, weiterhin Isobuten, Vinylaromaten wie beispielsweise Styrol, weiterhin In the context of the present invention, 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. In the context of the present invention, polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene and up to 50 mol% of at least one further comonomer, for example α-olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
(Meth)acrylsäure, Vinylacetat, Vinylpropionat, Ci-Cio-Alkylester der (Meth)acrylsäure, insbesondere Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, n-Butylacrylat, 2- Ethylhexylacrylat, n-Butylmethacrylat, 2-Ethylhexylmethacrylat, weiterhin Maleinsäure, Maleinsäureanhydrid und Itaconsäureanhydrid. Bei Polyethylen kann es sich um HDPE oder um LDPE handeln. (Meth) acrylic acid, vinyl acetate, vinyl propionate, Ci-Cio-alkyl esters of (meth) acrylic acid, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, further maleic acid, maleic anhydride and itaconic. Polyethylene may be HDPE or LDPE.
Im Rahmen der vorliegenden Erfindung wird unter Polypropylen nicht nur Homo-Polypropylen verstanden, sondern auch Copolymere des Propylens, die mindestens 50 mol-% Propylen ein- polymerisiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispielsweise Ethylen und a-Olefine wie Butylen, 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen und 1 - Penten. Bei Polypropylen handelt es sich vorzugsweise um isotaktisches oder um im Wesentlichen isotaktisches Polypropylen. Im Rahmen der vorliegenden Erfindung werden unter Polystyrol nicht nur Homopolymere des Styrols verstanden, sondern auch Copolymere mit Acrylnitril, 1 ,3-Butadien, (Meth)acrylsäure, Ci-Cio-Alkylester der (Meth)acrylsäure, Divinylbenzol, insbesondere 1 ,3-Divinylbenzol, 1 ,2- Diphenylethylen und a-Methylstyrol. In the context of the present invention, polypropylene is understood to mean not only homo-polypropylene, but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or substantially isotactic polypropylene. In the context of the present invention, 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.
Ein anderes bevorzugtes Bindemittel ist Polybutadien. Another preferred binder is polybutadiene.
Andere geeignete Bindemittel sind gewählt aus Polyethylenoxid (PEO), Cellulose, Carboxy- methylcellulose, Polyimiden und Polyvinylalkohol. Other suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimides and polyvinyl alcohol.
In einer Ausführungsform der vorliegenden Erfindung wählt man Bindemittel aus solchen (Co)polymeren, die ein mittleres Molekulargewicht Mw im Bereich von 50.000 bis 1 .000.000 g/mol, bevorzugt bis 500.000 g/mol aufweisen. Bei Bindemitteln kann es sich um vernetzte oder unvernetzte (Co)polymere handeln. In one embodiment of the present invention, binders are selected from those (co) polymers which have an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol, preferably up to 500,000 g / mol. Binders may be crosslinked or uncrosslinked (co) polymers.
In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Bindemittel aus halogenierten (Co)polymeren, insbesondere aus fluorierten (Co)polymeren. Dabei werden unter halogenierten bzw. fluorierten (Co)polymeren solche (Co)polymere verstanden, die mindestens ein (Co)monomer einpolymerisiert enthalten, das mindestens ein Halogenatom bzw. mindestens ein Fluoratom pro Molekül aufweist, bevorzugt mindestens zwei Halogenatome bzw. mindestens zwei Fluoratome pro Molekül. In a particularly preferred embodiment of the present invention, binders are selected from halogenated (co) polymers, in particular from fluorinated (co) polymers. Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which contain at least one (co) monomer in copolymerized form which has at least one halogen atom or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule.
Beispiele sind Polyvinylchlorid, Polyvinylidenchlorid, Polytetrafluorethylen, Polyvinylidenfluorid (PVdF), Tetrafluoroethylen-Hexafluorpropylen-Copolymere, Vinylidenfluorid-Hexafluorpropylen- Copolymere (PVdF-HFP), Vinylidenfluorid-Tetrafluorethylen-Copolymere, Perfluoralkylviny- lether-Copolymere, Ethylen-Tetrafluorethylen-Copolymere, Vinylidenfluorid-Chlortrifluorethylen- Copolymere und Ethylen-Chlorfluorethylen-Copolymere. Geeignete Bindemittel sind insbesondere Polyvinylalkohol und halogenierte (Co)polymere, beispielsweise Polyvinylchlorid oder Polyvinylidenchlorid, insbesondere fluorierte (Co)polymere wie Polyvinylfluorid und insbesondere Polyvinylidenfluorid und Polytetrafluorethylen. Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers. Suitable binders are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
Weiterhin kann Kathode (A) weitere an sich übliche Bestandteile aufweisen, beispielsweise ei- nen Stromableiter, der in Form eines Metalldrahts, Metallgitters, Metallnetzes, Streckmetalls, Metallblechs oder einer Metallfolie ausgestaltet sein kann. Als Metallfolien sind insbesondere Aluminiumfolien geeignet. Furthermore, cathode (A) may comprise further conventional components, for example a current conductor, which may be configured in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil. Aluminum foils are particularly suitable as metal foils.
In einer Ausführungsform der vorliegenden Erfindung weist Kathode (A) eine Dicke im Bereich von 25 bis 200 μηη, vorzugweise von 30 bis 100 μηη auf, bezogen auf die Dicke ohne Stromableiter. Erfindungsgemäße elektrochemische Zellen enthalten weiterhin mindestens eine Anode (B). In one embodiment of the present invention, cathode (A) has a thickness in the range of 25 to 200 μηη, preferably from 30 to 100 μηη, based on the thickness without Stromableiter. Inventive electrochemical cells also contain at least one anode (B).
In einer Ausführungsform der vorliegenden Erfindung kann man Anode (B) aus Anoden aus Kohlenstoff und Anoden, die Sn oder Si enthalten, wählen. Anoden aus Kohlenstoff kann man beispielsweise wählen aus Hart-Carbon, Soft Carbon, Graphen, Graphit und insbesondere Graphit, interkaliertem Graphit und Gemischen von zwei oder mehr der vorstehend genannten Kohlenstoffen. Anoden, die Sn oder Si enthalten, kann man beispielsweise wählen aus nanopartiku- lärem Si- bzw. Sn-Pulver, Si- bzw. Sn-Fasern, Kohlenstoff-Si- bzw. Kohlenstoff-Sn- Verbundwerkstoffen und Si-Metall- bzw. Sn-Metall-Legierungen. In one embodiment of the present invention, anode (B) may be selected from anodes of carbon and anodes containing Sn or Si. For example, carbon anodes may be selected from hard carbon, soft carbon, graphene, graphite, and especially graphite, intercalated graphite, and mixtures of two or more of the aforementioned carbons. Anodes containing Sn or Si can be selected, for example, from nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composites and Si-metal or Sn metal alloys.
Anode (B) kann ein oder mehrere Bindemittel aufweisen. Dabei kann man als Bindemittel ein oder mehr der vorstehend genannten Bindemittel wählen. Anode (B) may comprise one or more binders. In this case, one can choose as binder one or more of the aforementioned binders.
Weiterhin kann Anode (B) weitere an sich übliche Bestandteile aufweisen, beispielsweise einen Stromableiter, der in Form eines Metalldrahts, Metallgitters, Metallnetzes, Streckmetalls, oder einer Metallfolie oder eines Metallblechs ausgestaltet sein kann. Als Metallfolien sind insbesondere Kupferfolien geeignet. Furthermore, anode (B) may have further conventional components, for example a current conductor, which may be designed in the form of a metal wire, metal grid, metal mesh, expanded metal, or a metal foil or a metal sheet. As metal foils in particular copper foils are suitable.
In einer Ausführungsform der vorliegenden Erfindung weist Anode (B) eine Dicke im Bereich von 15 bis 200 μηη, vorzugweise von 30 bis 100 μηη auf, bezogen auf die Dicke ohne Stromableiter. In one embodiment of the present invention, anode (B) has a thickness in the range of 15 to 200 μηη, preferably from 30 to 100 μηη, based on the thickness without Stromableiter.
Erfindungsgemäße elektrochemische Zellen enthalten weiterhin Inventive electrochemical cells continue to contain
(C) mindestens eine Schicht, kurz auch Schicht (C) genannt, enthaltend (C) at least one layer, also called layer (C), containing
(a) mindestens einen Ionenaustauscher in partikulärer Form, kurz auch Ionenaustauscher (a) genannt, und  (a) at least one ion exchanger in particulate form, also called ion exchanger (a) for short, and
(b) mindestens einen Binder, kurz auch Binder (b) oder auch Bindemittel (b) genannt. Ionenaustauscher (a) sind als solche bekannt. Ionenaustauscher können im Rahmen der vorliegenden Erfindung einen mittleren Partikel-Durchmesser im Bereich von 0,1 bis 50 μηη, bevorzugt 1 bis 10 μηη aufweisen. (b) at least one binder, also called binder (b) or binder (b) for short. Ion exchangers (a) are known as such. In the context of the present invention, ion exchangers can have an average particle diameter in the range from 0.1 to 50 μm, preferably from 1 to 10 μm.
In einer Ausführungsform der vorliegenden Erfindung wählt man Ionenaustauscher in partikulä- rer Form aus kationischen Kunstharz-Ionenaustauschern (z.B. Polystyrolkunstharz oder Polyac- rylat), wobei die aktive Gruppe eine anionische Gruppe ist, beispielsweise Sulfonsäuregruppe oder Carbonsäuregruppe, weiterhin aus Molekularsieben, Zeolithen und Lithium-haltigen Molekularsieben. Molekularsiebe werden im Folgenden vorzugsweise aus natürlichen und synthetischen Zeolithen gewählt, die in Form von Kugeln (Perlen), als Pulver oder Stäbchen vorliegen können. Bevorzugt setzt man Molekularsieb 4Ä, besonders bevorzugt Molekularsieb 3Ä ein. lonentauscher kann man als Formkörper, beispielsweise in Form von Perlen oder Stäbchen, oder als Pulver einsetzen. Bevorzugt sind Formkörper wie insbesondere Pulver. In one embodiment of the present invention, ionic exchangers in particulate form are selected from cationic synthetic resin ion exchangers (eg polystyrene resin or polyacrylate), the active group being an anionic group, for example sulfonic acid group or carboxylic acid group, furthermore consisting of molecular sieves, zeolites and lithium containing molecular sieves. In the following, molecular sieves are preferably selected from natural and synthetic zeolites, which may be in the form of spheres (beads), powders or rods. Preference is given to molecular sieve 4A, more preferably molecular sieve 3A. Ion exchangers can be used as shaped articles, for example in the form of beads or rods, or as powders. Preference is given to moldings, in particular powders.
In einer Ausführungsform der vorliegenden Erfindung setzt man kationischen lonentauscher ein. In one embodiment of the present invention, cationic ion exchangers are used.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Ionenaustauscher aus zumindest partiell lithiierten lonentauschern bzw. zumindest partiell lithiierte Molekularsieben. Unter zumindest partiell lithiierten lonentauschern bzw. mindestens partiell lithiierten Molekularsieben versteht man solche kationischen lonentauscher, die H+ und/oder Na+ oder K+ mög- liehst weitgehend durch Li+ substituieren. In a preferred embodiment of the present invention, ion exchangers are selected from at least partially lithiated ion exchangers or at least partially lithiated molecular sieves. At least partially lithiated ion exchangers or at least partially lithiated molecular sieves are understood to mean those cationic ion exchangers which largely replace H + and / or Na + or K + by Li + .
In einer Ausführungsform der vorliegenden Erfindung wählt man Binder (b) aus solchen Bindern, wie im Zusammenhang mit Bindemittel für die Kathode(n) (A) beschrieben. In einer bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Bindemittel (b) aus Polyvinylalkohol, Styrol-Butadien-Kautschuk, Polyacrylnitril, Carboxymethylcellulose und fluorhaltigen (Co)polymeren. In one embodiment of the present invention, binder (b) is selected from such binders as described in connection with binder for the cathode (s) (A). In a preferred embodiment of the present invention, binder (b) is selected from polyvinyl alcohol, styrene-butadiene rubber, polyacrylonitrile, carboxymethyl cellulose and fluorine-containing (co) polymers.
In einer Ausführungsform der vorliegenden Erfindung sind Binder (b) sowie Bindemittel für Ka- thode und für Anode, so vorhanden, jeweils gleich. In one embodiment of the present invention, binders (b) as well as binders for cathode and for anode, if present, are the same in each case.
In einer anderen Ausführungsform unterscheidet sich Binder (b) von Bindemittel für Kathode (A) und/oder Bindemittel für Anode (B), oder Bindemittel für Anode (B) und Bindemittel für Kathode (A) sind verschieden. In another embodiment, binder (b) differs from binder for cathode (A) and / or binder for anode (B), or binder for anode (B) and binder for cathode (A) are different.
In einer Ausführungsform der vorliegenden Erfindung dient Schicht (C) als Separator. Ein derartiger Separator kann beispielsweise ein Vlies enthalten, das anorganischer oder organischer Natur sein kann, oder eine poröse Kunststoffschicht, beispielsweise eine Polyolefinmembran, insbesondere eine Polyethylen- oder eine Polypropylenmembran. Vorzugsweise enthält Schicht (C) dann zwei poröse Kunststoffschichten, zwischen denen Ionenaustauscher (a) eingebettet ist. In one embodiment of the present invention, layer (C) serves as a separator. Such a separator may contain, for example, a nonwoven which may be of inorganic or organic nature, or a porous plastic layer, for example a polyolefin membrane, in particular a polyethylene or a polypropylene membrane. Preferably, layer (C) then contains two porous plastic layers, between which ion exchanger (a) is embedded.
In einer anderen Ausführungsform der vorliegenden Erfindung ist Ionenaustauscher (a) in eine Lage von Bindemittel auf Kathode (A) oder auf Anode (B) eingefügt, beispielsweise eingedrückt. In another embodiment of the present invention, ion exchanger (a) is inserted in a layer of binder on the cathode (A) or on the anode (B), for example pressed in.
In einer Ausführungsform der vorliegenden Erfindung kann Schicht (C) weiterhin ein Vlies (c) enthalten. Vlies (c) kann organischer oder vorzugsweise anorganischer Natur sein. Beispiele für organische Vliese (c) sind Polyester-Vliese, insbesondere Polyethylenterephthalat-Vliese (PET- Vliese), Polybutylenterephthalat-Vliese (PBT-Vliese), Polyimid-Vliese, Polyethylen- und Po- lypropylen-Vliese, PVdF-Vliese und PTFE-Vliese. In one embodiment of the present invention, layer (C) may further include a nonwoven fabric (c). Fleece (c) may be organic or preferably inorganic in nature. Examples of organic nonwovens (c) are polyester nonwovens, in particular polyethylene terephthalate nonwovens (PET nonwovens), polybutylene terephthalate nonwovens (PBT nonwovens), polyimide nonwovens, polyethylene and polypropylene nonwovens, PVdF nonwovens and PTFE fleeces.
Beispiele für anorganische Vliese (c) sind Glasfaservliese und Keramikfaservliese. In einer Ausführungsform der vorliegenden Erfindung weist Schicht (C) eine Dicke im Bereich von 0,1 μηη bis 250 μηη, bevorzugt 1 μηη bis 50 μηη und besonders bevorzugt mindestens 9 μηη auf. Examples of inorganic nonwovens (c) are glass fiber nonwovens and ceramic fiber nonwovens. In one embodiment of the present invention, layer (C) has a thickness in the range from 0.1 μm to 250 μm, preferably 1 μm to 50 μm, and particularly preferably at least 9 μm.
Erfindungsgemäße Zellen können weiterhin an sich übliche Bestandteile aufweisen, beispielsweise Leitsalz, nicht-wässriges Lösungsmittel, weiterhin Kabelverbindungen und Gehäuse. Cells according to the invention may further comprise customary constituents, for example conductive salt, nonaqueous solvent, furthermore cable connections and housings.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße elektrische Zellen mindestens ein nicht-wässriges Lösungsmittel, das bei Zimmertemperatur flüssig oder fest sein kann, bevorzugt gewählt aus Polymeren, cyclischen oder nicht-cyclischen Ethern, cyclischen und nicht-cyclischen Aeetalen und cyclischen oder nicht cyclischen organischen Carbo- naten. Beispiele für geeignete Polymere sind insbesondere Polyalkylenglykole, bevorzugt P0IV-C1-C4- alkylenglykole und insbesondere Polyethylenglykole. Dabei können Polyethylenglykole bis zu 20 mol-% ein oder mehrere Ci-C4-Alkylenglykole einpolymerisiert enthalten. Vorzugsweise handelt es sich bei Polyalkylenglykolen um zweifach mit Methyl oder Ethyl verkappte Polyalkylenglykole. In one embodiment of the present invention, 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 ethers and cyclic or non-cyclic organic Carbonates. Examples of suitable polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols. Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form. Preferably, polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl.
Das Molekulargewicht Mw von geeigneten Polyalkylenglykolen und insbesondere von geeigneten Polyethylenglykolen kann mindestens 400 g/mol betragen. The molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
Das Molekulargewicht Mw von geeigneten Polyalkylenglykolen und insbesondere von geeigne- ten Polyethylenglykolen kann bis zu 5.000.000 g/mol betragen, bevorzugt bis zu 2.000.000 g/mol betragen 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
Beispiele für geeignete nicht-cyclische Ether sind beispielsweise Diisopropylether, Di-n- Butylether, 1 ,2-Dimethoxyethan, 1 ,2-Diethoxyethan, bevorzugt ist 1 ,2-Dimethoxyethan. Examples of suitable non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
Beispiele für geeignete cyclische Ether sind Tetrahydrofuran und 1 ,4-Dioxan. Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
Beispiele für geeignete nicht-cyclische Acetale sind beispielsweise Dimethoxymethan, Dietho- xymethan, 1 ,1 -Dimethoxyethan und 1 ,1-Diethoxyethan. Examples of suitable non-cyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
Beispiele für geeignete cyclische Acetale sind 1 ,3-Dioxan und insbesondere 1 ,3-Dioxolan. Examples of suitable cyclic acetals are 1, 3-dioxane and in particular 1, 3-dioxolane.
Beispiele für geeignete nicht-cyclische organische Carbonate sind Dimethylcarbonat, Ethylme- thylcarbonat und Diethylcarbonat. Examples of suitable non-cyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
Beispiele für geeignete cyclische organische Carbonate sind Verbindungen der allgemeinen Formeln (X) und (XI) Examples of suitable cyclic organic carbonates are compounds of the general formulas (X) and (XI)
bei denen R1, R2 und R3 gleich oder verschieden sein können und gewählt aus Wasserstoff und Ci-C4-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, wobei vorzugsweise R2 und R3 nicht beide tert.-Butyl sind. in which R 1 , R 2 and R 3 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 2 and R 3 are not both tert-butyl.
In besonders bevorzugten Ausführungsformen ist R1 Methyl und R2 und R3 sind jeweils Wasserstoff, oder R1, R2 und R3 sind jeweils gleich Wasserstoff. Ein anderes bevorzugtes cyclisches organisches Carbonat ist Vinylencarbonat, Formel (XII). In particularly preferred embodiments, 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 (XII).
Vorzugsweise setzt man das oder die Lösungsmittel im so genannten wasserfreien Zustand ein, d.h. mit einem Wassergehalt im Bereich von 1 ppm bis 0,1 Gew.-%, bestimmbar beispielsweise durch Karl-Fischer-Titration. Preferably, 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.
Erfindungsgemäße elektrochemische Zellen enthalten weiterhin mindestens ein Leitsalz. Geeignete Leitsalze sind insbesondere Lithiumsalze. Beispiele für geeignete Lithiumsalze sind LiPF6, LiBF4, UCIO4, LiAsF6, UCF3SO3, LiC(CnF2n+iS02)3, Lithiumimide wie LiN(CnF2n+iS02)2, wobei n eine ganze Zahl im Bereich von 1 bis 20 ist, LiN(S02F)2, Li2SiFe, LiSbF6, LiAICU, und Salze der allgemeinen Formel (CnF2n+iS02)mXLi, wobei m wie folgt definiert ist: Inventive electrochemical cells also contain at least one conductive salt. Suitable conductive salts are in particular lithium salts. Examples of suitable lithium salts are LiPF 6, LiBF 4, UCIO4, LiAsF 6, UCF3SO3, LiC (CnF 2n + IS02) 3, lithium imides such as LiN (CnF 2 n + IS02) 2, where n is an integer ranging from 1 to 20 , LiN (SO 2 F) 2, Li 2 SiFe, 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:
m = 1 , wenn X gewählt wird aus Sauerstoff und Schwefel, m = 1, if X is selected from oxygen and sulfur,
m = 2, wenn X gewählt wird aus Stickstoff und Phosphor, und m = 3, wenn X gewählt wird aus Kohlenstoff und Silizium. m = 2 when X is selected from nitrogen and phosphorus, and m = 3, when X is selected from carbon and silicon.
Bevorzugte Leitsalze sind gewählt aus LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, Preferred conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
LiCI04, und besonders bevorzugt sind LiPF6 und LiN(CFsS02)2. LiCl 4 , and particularly preferred are LiPF 6 and LiN (CF 2 SO 2) 2.
Erfindungsgemäße elektrochemische Zellen enthalten weiterhin ein Gehäuse, das beliebige Form haben kann, beispielsweise quaderförmig oder die Form eines Zylinders. In einer anderen Ausführungsform haben erfindungsgemäße elektrochemische Zellen die Form eines Prismas. In einer Variante wird als Gehäuse eine als Beutel ausgearbeitete Metall-Kunststoff- Verbundfolie eingesetzt. Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example cuboid or the shape of a cylinder. In another embodiment, electrochemical cells according to the invention have the shape of a prism. In one variant, a metal-plastic composite film prepared as a bag is used as the housing.
Erfindungsgemäße elektrochemische Zellen liefern eine hohe Spannung und zeichnen sich aus durch eine hohe Energiedichte und gute Stabilität aus. Insbesondere zeichnen sich erfindungsgemäße elektrochemische Zellen durch einen nur sehr geringen Kapazitätsverlust bei längerem Gebrauch und wiederholten Zyklieren aus. Inventive electrochemical cells provide a high voltage and are characterized by a high energy density and good stability. In particular, electrochemical cells according to the invention are characterized by only a very small loss of capacity with prolonged use and repeated cycling.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen elektrochemischen Zellen in Lithium-Ionen-Batterien. Ein weiterer Gegenstand der vorliegenden Erfindung sind Lithium-Ionen-Batterien, enthaltend mindestens eine erfindungsgemäße elektrochemische Zelle. Erfindungsgemäße elektrochemische Zellen lassen sich in erfindungsgemäßen Lithium-Ionen-Batterien sich miteinander kombinieren, beispielsweise in Reihenschaltung oder in Parallelschaltung. Reihenschaltung ist bevorzugt. Another object of the present invention is the use of electrochemical cells according to the invention in lithium-ion batteries. Another object of the present invention are lithium-ion batteries, containing at least one electrochemical cell according to the invention. Inventive electrochemical cells can be combined with one another in lithium-ion batteries according to the invention, for example in series connection or in parallel connection. Series connection is preferred.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemä- ßen Lithium-Ionen-Batterien in Geräten, insbesondere in mobilen Geräten. Beispiele für mobile Geräte sind Fahrzeuge, beispielsweise Automobile, Zweiräder, Flugzeuge oder Wasserfahrzeuge wie Boote oder Schiffe. Andere Beispiele für mobile Geräte sind solche, die man selber bewegt, beispielsweise Computer, insbesondere Laptops, Telefone oder elektrische Handwerkszeuge, beispielsweise aus dem Bereich des Bauens, insbesondere Bohrmaschinen, Ak- kubohrschrauber oder Akku-Tacker. Another object of the present invention is the use of inventive lithium-ion batteries in devices, especially in mobile devices. Examples of mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships. Other examples of mobile devices are those that you move yourself, for example computers, especially laptops, telephones or electrical tools, for example in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
Die Verwendung von erfindungsgemäßen Lithium-Ionen-Batterien in Geräten bietet den Vorteil einer längeren Laufzeit vor dem Nachladen sowie einen geringeren Kapazitätsverlust bei längerer Laufzeit. Wollte man mit elektrochemischen Zellen mit geringerer Energiedichte eine gleiche Laufzeit verwirklichen, so müsste man ein höheres Gewicht für elektrochemische Zellen in Kauf nehmen. The use of lithium-ion batteries in devices according to the invention offers the advantage of a longer running time before recharging as well as a lower capacity loss with a longer running time. If one wanted to realize an equal running time with electrochemical cells with a lower energy density, then one would have to accept a higher weight for electrochemical cells.
Die Erfindung wird durch Arbeitsbeispiele erläutert. The invention will be explained by working examples.
Angaben in Prozent beziehen sich jeweils auf Gew.-%, wenn nicht ausdrücklich anders ange- geben. I. Herstellung von erfindungsgemäßen Schichten (C), die als Separator eingesetzt werden können Percentages are by weight in each case, unless expressly stated otherwise. I. Preparation of layers (C) according to the invention which can be used as a separator
1.1 Herstellung eines erfindungsgemäßen Separators (C.1 ) Aus einem Glasfaservlies (Whatman, 260 μηη Dicke) stanzte man Scheiben mit 13 mm Durchmesser aus und trocknete sie im Trockenschrank bei 120°C für mehrere Stunden. Danach ü- berführte man die Glasfaservlies-Scheiben in eine Argon-gefüllte Glove-box. Man teilte jede Glasfaservlies-Scheiben in zwei Teile, so dass aus einer Glasfaservlies-Scheibe zwei Glasfaservlies-Scheiben (c.1 ) entstanden, die je ca. 130 μηη dick waren.  1.1 Preparation of a separator (C.1) according to the invention From a glass fiber fleece (Whatman, 260 μηη thickness) punched out discs with 13 mm diameter and dried in a drying oven at 120 ° C for several hours. Thereafter, the glass fiber nonwoven discs were transferred to an argon-filled glove box. Each glass fiber nonwoven disc was divided into two parts, so that from a glass fiber fleece disc two glass fiber fleece discs (c.1) were formed, each about 130 μηη thick.
Man trocknete lithiiertes Molsieb (a.1 ) (LITHIUM SILIPORITE® G5000, Ceca) über einen Zeitraum von 16 Stunden bei 200°C im Vakuumtrockenschrank. Danach verrieb man das so getrocknete lithiierte Molsieb mit Mörser und Pistill zu einem feinen Pulver, das man durch ein Sieb mit einer Maschenweite von 32 μηη siebte. Man vermischte das gesiebte feine Pulver an- schließend im Gewichstverhältnis 9:1 mit Polyvinylidenfluorid, kommerziell erhältlich als Kynar® FLEX 2801 der Fa. Arkema, (b.1 ), und gab danach tropfenweise N-Methylpyrrolidon zu, bis man eine zähe Paste erhielt. Die so erhaltene zähe Paste rührte man über einen Zeitraum von 16 Stunden. Man räkelte die so erhaltene Paste gleichmäßig auf der Oberseite der zwei Glasfaservlies- Scheiben (c.1 ), so dass eine Belegung von je 15 mg/cm2 erreicht wurde. Man legte die zwei Molsieb-bedeckten Glasfaservlies-Scheiben sandwichartig zu einem Separator/Molsieb/Separa- tor-Komposit zusammen. Man erhielt erfindungsgemäße Schicht (C.1 ). I.2 Herstellung eines erfindungsgemäßen Separators (C.2) The lithiated molecular sieve (a.1) (LITHIUM SILIPORITE® G5000, Ceca) was dried for 16 hours at 200 ° C. in a vacuum oven. Thereafter, the thus dried lithiated Molsieb with mortar and pestle was crushed to a fine powder, which was seventh through a sieve with a mesh size of 32 μηη. The sieved fine powder was then mixed in a weight ratio of 9: 1 with polyvinylidene fluoride, commercially available as Kynar® FLEX 2801 from Arkema, (b.1), followed by dropwise addition of N-methylpyrrolidone until a viscous paste was obtained , The viscous paste thus obtained was stirred for a period of 16 hours. The resulting paste was stretched evenly on the top of the two glass fiber fleece discs (c.1), so that an occupancy of 15 mg / cm 2 was achieved. The two molecular sieve-covered glass fiber nonwoven discs were sandwiched together to form a separator / molecular sieve / separator composite. Inventive layer (C.1) was obtained. I.2 Production of a Separator According to the Invention (C.2)
Versuch 1.1 wurde wiederholt, jedoch verwendete man statt zwei Scheiben (c.1 ) zwei 20 μηη dicke PET-Vlies-Scheiben (c.2), kommerziell erhältlich als Vlies„PES20" der Fa. APODIS Filtertechnik OHG. Man erhielt erfindungsgemäße Schicht (C.2). Experiment 1.1 was repeated, but instead of two disks (c.1), two 20 μηη thick PET nonwoven disks (c.2) were used, commercially available as fleece "PES20" from APODIS Filtertechnik OHG. C.2).
I.3 Vergleichsbeispiel I.3 comparative example
Der Versuch aus Beispiel 1.1 wurde unter denselben Bedingungen wiederholt, jedoch wurde die das lithiierte Molsieb (a.1 ) weggelassen. Man erhielt Vergleichsschicht (V-C.3). The experiment of Example 1.1 was repeated under the same conditions, but the lithiated molecular sieve (a.1) was omitted. Comparative layer (V-C.3) was obtained.
II. Herstellung von erfindungsgemäßen elektrochemischen Zellen und Testung II. Production of electrochemical cells according to the invention and testing
Man verwendete stets folgende Elektroden: Kathode (A.1 ): man verwendete eine Lithium-Nickel-Mangan-Spinell-Elektrode, die wie folgt hergestellt wurden. Man vermischte miteinander: The following electrodes were always used: Cathode (A.1): a lithium-nickel-manganese spinel electrode was used which was prepared as follows. One mixed with each other:
85% LiMni,5Ni0,5O4 6% PVdF, kommerziell erhältlich als Kynar Flex® 2801 der Arkema Group, 85% LiMni, 5 Ni 0 , 5 O4 6% PVdF, commercially available as Kynar Flex® 2801 from the Arkema Group,
6% Ruß, BET-Oberfläche von 62 m2/g, kommerziell erhältlich als„Super P Li" der Firma Timcal,6% carbon black, BET surface area of 62 m 2 / g, commercially available as "Super P Li" from Timcal,
3% Graphit, kommerziell erhältlich als KS6 der Fa. Timcal; 3% graphite, commercially available as KS6 from Timcal;
in einem verschraubbaren Gefäß. Unter Rühren versetzte man mit so viel N-Methyl-Pyrrolidon, bis man eine zähe klumpenfreie Paste erhalten hatte. Man rührte 16 Stunden. in a screw-in container. With stirring, it was mixed with so much N-methyl-pyrrolidone until a tough lump-free paste had been obtained. It was stirred for 16 hours.
Dann räkelte man die so erhältliche Paste auf 20 μηη dicke Aluminiumfolie auf und trocknete 16 Stunden lang in einem Vakuumtrockenschrank bei 120°C. Die Dicke der Beschichtung betrug nach dem Trocknen 30 μηη. Anschließend stanzte man kreisscheibenförmige Segmente aus, Durchmesser: 12 mm. Then the so-available paste was lazelte on 20 μηη thick aluminum foil and dried for 16 hours in a vacuum oven at 120 ° C. The thickness of the coating was 30 μηη after drying. Then punched out circular disk-shaped segments, diameter: 12 mm.
Anode (B.1 ): Man vermischte miteinander Anode (B.1): One mixed with each other
91 % Graphit ConocoPhillips C5 91% graphite ConocoPhillips C5
6% PVdF, kommerziell erhältlich als Kynar Flex® 2801 der Arkema Group,  6% PVdF, commercially available as Kynar Flex® 2801 from the Arkema Group,
3% Ruß, BET-Oberfläche von 62 m2/g, kommerziell erhältlich als„Super P Li" der Firma Timcal In einem verschraubbaren Gefäß. Unter Rühren versetzte man mit so viel N-Methyl-Pyrrolidon, bis man eine zähe klumpenfreie Paste erhalten hatte. Man rührte 16 Stunden. 3% carbon black, BET surface area of 62 m 2 / g, commercially available as "Super P Li" from Timcal in a screw-on vessel With stirring, add so much N-methyl-pyrrolidone until a viscous lump-free paste is obtained One stirred for 16 hours.
Dann räkelte man die so erhältliche Paste auf 20 μηη dicke Kupferfolie auf und trocknete 16 Stunden lang in einem Vakuumtrockenschrank bei 120°C. Die Dicke der Beschichtung betrug nach dem Trocknen 35 μηη. Anschließend stanzte man kreisscheibenförmige Segmente aus, Durchmesser: 12 mm. Then, the so-available paste was lazelte on 20 μηη thick copper foil and dried for 16 hours in a vacuum oven at 120 ° C. The thickness of the coating was after drying 35 μηη. Then punched out circular disk-shaped segments, diameter: 12 mm.
11.1 Herstellung einer erfindungsgemäßen elektrochemischen Zelle EZ.1 und Testung 11.1 Production of an Electrochemical Cell EZ.1 According to the Invention and Testing
Man verwendete stets folgenden Elektrolyten: The following electrolytes were always used:
1 M Lösung von LiPF6 in wasserfreiem Ethylencarbonat-Ethylmethylcarbonat-Gemisch (Gewichtsanteile 1 :1 ) Die nach 1.1 hergestellte erfindungsgemäße Schicht (C.1 ) wurde als Separator eingesetzt und dazu in einer Argon-gefüllten Glove-box mit Elektrolyt betropft und zwischen einer Kathode (A.1 ) und einer Anode (B.1 ) positioniert, so dass sowohl die Anode als auch die Kathode direkten Kontakt zum Separator hatte. Man setzte Elektrolyt zu und erhielt erfindungsgemäße elektrochemische Zellen EZ.1 . Die elektrochemische Untersuchung erfolgte zwischen 4,25 V und 4,8 V in Drei-Elektroden-Swagelokzellen.  1 M solution of LiPF6 in anhydrous ethylene carbonate-ethylmethyl carbonate mixture (weight proportions 1: 1) The layer (C.1) according to the invention prepared according to 1.1 was used as a separator and dripped with an electrolyte in an argon-filled glove box and between a cathode (A.1) and an anode (B.1), so that both the anode and the cathode were in direct contact with the separator. Electrolyte was added and electrochemical cells EZ.1 according to the invention were obtained. Electrochemical testing was between 4.25V and 4.8V in three-electrode Swagelok cells.
Die ersten zwei Zyklen wurden zwecks Formierung bei 0,2C-Rate gefahren; die Zyklen Nr. 3 bis Nr. 50 wurden bei 1 C-Rate gezykelt. Das Laden bzw. Entladen der Zelle wurde mit Hilfe eines „MACCOR Battery Tester" bei Raumtemperatur durchgeführt. The first two cycles were run at 0.2C rate for formation; Cycles # 3 through # 50 were cycled at 1 C rate. The charging or discharging of the cell was carried out with the aid of a "MACCOR Battery Tester" at room temperature.
Es konnte gezeigt werden, dass die Batterie-Kapazität über wiederholtes Laden und Entladen stabil blieb, und zwar nahe am theoretischen Wert von 100%. II.2 Herstellung einer erfindungsgemäßen elektrochemischen Zelle EZ.2 und Testung It could be shown that the battery capacity remained stable over repeated charging and discharging, close to the theoretical value of 100%. II.2 Production of an Electrochemical Cell EZ.2 According to the Invention and Testing
Man ging vor wie unter 11.1 beschrieben, setzte jedoch Schicht (C.2) statt Schicht (C.1 ) ein. Man erhielt erfindungsgemäße elektrochemische Zelle EZ.2, die man analog zu 11.1 testete. The procedure was as described under 11.1, but using layer (C.2) instead of layer (C.1). This gave inventive electrochemical cell EZ.2, which was tested analogously to 11.1.
II.3 Herstellung einer nicht erfindungsgemäßen elektrochemischen Zelle V-EZ.3 und Testung II.3 Production of a non-inventive electrochemical cell V-EZ.3 and testing
Man ging vor wie unter 11.1 beschrieben, setzte jedoch Schicht (V-C.3) statt Schicht (C.1 ) ein. Man erhielt elektrochemische Zelle V-EZ.3, die man analog zu 11.1 testete. The procedure was as described under 11.1, but using layer (V-C.3) instead of layer (C.1). Electrochemical cell V-EZ.3 was obtained, which was tested analogously to 11.1.
Ergebnisse: Results:
EZ. 1 und EZ.2 konnten über 50 Zyklen sehr gut stabil geladen und entladen werden. Die Kapazitäten nahm dabei kaum ab (siehe Abb. 2 am Beispiel von EZ.2). Es konnte gezeigt werden, dass die Batterie-Kapazität nach 50 Zyklen von anfänglich 96 mAh/g um 7 mAh/g auf 89 mAh/g abfiel, was einem Kapazitätsverlust von 7,7% entspricht. Die Lade-/Entladeeffizienz erreichte Werte von über 99%. EZ. 1 and EZ.2 could be charged and discharged very well over 50 cycles. The capacity hardly decreased (see Fig. 2 using the example of EZ.2). It could be shown that the battery capacity dropped from 7 mAh / g to 89 mAh / g after 50 cycles from initially 96 mAh / g, which corresponds to a capacity loss of 7.7%. The charging / discharging efficiency reached values of over 99%.
Die elektrochemische Zelle V-EZ.3 konnte zwar ebenfalls über mehrere Zyklen geladen und entladen werden, jedoch nahm die Kapazität stärker ab als bei EZ.1 . Es konnte gezeigt werden, dass die Batterie-Kapazität nach 50 Zyklen von anfänglich 95 mAh/g um 22 mAh/g auf 73 mAh/g abfiel, was einem Kapazitätsverlust von 23,2% entspricht. Die Lade-/Entladeeffizienz erreichte Werte von ca. 98%. Although the electrochemical cell V-EZ.3 could also be charged and discharged over several cycles, the capacity decreased more than with EZ.1. It could be shown that after 50 cycles the battery capacity dropped from initially 95 mAh / g by 22 mAh / g to 73 mAh / g, which corresponds to a capacity loss of 23.2%. The charging / discharging efficiency reached values of about 98%.
Fig. 1 zeigt Lade-/Entladekapazität (linke Achse, durchgezogene Linie) und Lade- /Entladeeffizienzen (rechte Achse, gepunktete Linie) der erfindungsgemäßen Zelle EZ.2 Fig. 1 shows charge / discharge capacity (left axis, solid line) and charge / discharge efficiencies (right axis, dotted line) of the cell EZ.2 of the present invention

Claims

Patentansprüche claims
Elektrochemische Zelle, enthaltend Electrochemical cell containing
(A) mindestens eine Kathode, enthaltend mindestens ein Lithiumionen-haltiges Ü- bergangsmetalloxid, das als Übergangsmetall Mangan enthält,  (A) at least one cathode, comprising at least one lithium-ion-containing transition metal oxide which contains manganese as the transition metal,
(B) mindestens eine Anode, und  (B) at least one anode, and
(C) mindestens eine Schicht, enthaltend  (C) at least one layer containing
(a) mindestens einen Ionenaustauscher in partikulärer Form,  (a) at least one ion exchanger in particulate form,
(b) mindestens einen Binder.  (b) at least one binder.
Elektrochemische Zelle nach Anspruch 1 , dadurch gekennzeichnet, dass man Lithiumio nen-haltiges Übergangsmetalloxid wählt aus Mangan-haltigen Spinellen und Mangan- haltigen Übergangsmetalloxiden mit Schichtstruktur. Electrochemical cell according to claim 1, characterized in that lithium-ion-containing transition metal oxide is selected from manganese-containing spinels and manganese-containing transition metal oxides having a layer structure.
Elektrochemische Zelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man Mangan-haltige Spinelle wählt aus solchen der Formel (I) wobei die Variablen wie folgt definiert sind: Electrochemical cell according to Claim 1 or 2, characterized in that manganese-containing spinels are selected from those of the formula (I) where the variables are defined as follows:
0,9 < a < 1 ,3 0.9 <a <1, 3
0 < b < 0,6 0 <b <0.6
-0,1 < d < 0,4, und -0,1 <d <0,4, and
M1 gewählt aus einem oder mehreren Elementen, gewählt aus AI, Mg, Ca, Na, B, Mo, W und Übergangsmetallen der ersten Periode des Periodensystems der Elemente. M 1 selected from one or more elements selected from Al, Mg, Ca, Na, B, Mo, W and transition metals of the first period of the periodic table of the elements.
Elektrochemische Zelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man Mangan-haltige Übergangsmetalloxide mit Schichtstruktur wählt aus solchen der Formel (Ii) wobei die Variablen wie folgt definiert sind: Electrochemical cell according to Claim 1 or 2, characterized in that manganese-containing transition metal oxides having a layer structure are selected from those of the formula (Ii) where the variables are defined as follows:
0 < t < 0,3 und M2 gewählt aus AI, Mg, B, Mo, W, Na, Ca und Übergangsmetallen der ersten Periode des Periodensystems der Elemente, wobei das oder mindestens ein Übergangsmetall Mangan ist. 0 <t <0.3 and M 2 selected from Al, Mg, B, Mo, W, Na, Ca and transition metals of the first period of the Periodic Table of the Elements, wherein the or at least one transition metal is manganese.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Anode (B) gewählt wird aus Anoden aus Kohlenstoff und Anoden, die Sn oder Si enthalten. Electrochemical cell according to one of claims 1 to 4, characterized in that anode (B) is selected from anodes of carbon and anodes containing Sn or Si.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass Ionenaustauscher in partikulärer Form gewählt wird aus Molekularsieben, Zeolithen und Lithium-haltigen Molekularsieben. Electrochemical cell according to one of claims 1 to 5, characterized in that the ion exchanger in particulate form is selected from molecular sieves, zeolites and lithium-containing molecular sieves.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass Schicht (C) eine Dicke im Bereich von 0,1 μηη bis 250 μηη aufweist. Electrochemical cell according to one of claims 1 to 6, characterized in that layer (C) has a thickness in the range of 0.1 μηη to 250 μηη.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es sich bei Schicht (C) um einen Separator handelt. Electrochemical cell according to one of Claims 1 to 7, characterized in that layer (C) is a separator.
Elektrochemische Zelle nach Anspruch 8, dadurch gekennzeichnet, dass Schicht (C) zusätzlich ein Vlies (c) enthält. Electrochemical cell according to claim 8, characterized in that layer (C) additionally contains a fleece (c).
Elektrochemische Zelle nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass Schicht (C) eine mittlere Dicke im Bereich von 9 bis 50 μηη aufweist. Electrochemical cell according to claim 8 or 9, characterized in that layer (C) has an average thickness in the range of 9 to 50 μηη.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass Schicht (C) die Kathode (A) oder den Separator oder die Anode (B) auf zumindest einer Seite bedeckt. Electrochemical cell according to one of claims 1 to 10, characterized in that layer (C) covers the cathode (A) or the separator or the anode (B) on at least one side.
Elektrochemische Zelle nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man Bindemittel (b) wählt aus Polyvinylalkohol, Styrol-Butadien-Kautschuk, Polyac- rylnitril, Carboxymethylcellulose und fluorhaltigen (Co)polymeren. Electrochemical cell according to one of claims 1 to 10, characterized in that one selects binder (b) from polyvinyl alcohol, styrene-butadiene rubber, polyacrylonitrile, carboxymethyl cellulose and fluorine-containing (co) polymers.
Verwendung von elektrochemischen Zellen nach einem der Ansprüche 1 bis 12 in Lithium-Ionen-Batterien. Use of electrochemical cells according to any one of claims 1 to 12 in lithium-ion batteries.
Lithium-Ionen-Batterie, enthaltend mindestens eine elektrochemische Zelle nach einem der Ansprüche 1 bis 12. Lithium-ion battery containing at least one electrochemical cell according to one of claims 1 to 12.
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