EP2742552A1 - Cellules électrochimiques - Google Patents

Cellules électrochimiques

Info

Publication number
EP2742552A1
EP2742552A1 EP12822507.5A EP12822507A EP2742552A1 EP 2742552 A1 EP2742552 A1 EP 2742552A1 EP 12822507 A EP12822507 A EP 12822507A EP 2742552 A1 EP2742552 A1 EP 2742552A1
Authority
EP
European Patent Office
Prior art keywords
lithium
layer
transition metal
electrochemical cell
ion
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Withdrawn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
EP12822507.5A
Other languages
German (de)
English (en)
Other versions
EP2742552A4 (fr
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 EP12822507.5A priority Critical patent/EP2742552A4/fr
Publication of EP2742552A1 publication Critical patent/EP2742552A1/fr
Publication of EP2742552A4 publication Critical patent/EP2742552A4/fr
Withdrawn legal-status Critical Current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
    • 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
    • H01M50/409—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—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
    • H01M50/463—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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to electrochemical cells containing
  • (D) at least one electrically non-conductive, porous and ion-permeable layer, which is positioned between the cathode (A) and layer (C), and at least one electrically non-conductive, porous and ion-permeable layer between anode (B) and layer (C ) is positioned.
  • the present invention relates to the use of electrochemical cells according to the invention, their preparation and a special separator for the separation of a cathode and an anode in an electrochemical cell.
  • 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.
  • a relatively high proportion of manganese for example in electrochemical cells with a manganese-containing spinel electrode and a graphite anode, one often observed a strong loss of capacity within a relatively short time.
  • graphite anodes as counterelectrodes, 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 optionally partly of inorganic material. Although such separators can be used to avoid short circuits caused by metal dendrites. In WO 2009/033627, however, no long-term cyclization experiments are disclosed.
  • WO 201 1/024149 discloses lithium-ion batteries containing an alkali metal such as lithium between the cathode and anode, which serves as a scavenger of unwanted by-products or impurities and is referred to as a scavenger. Both in the production of the secondary battery cells and in a later recycling of the disused cells due to the presence of highly reactive alkali metal appropriate safety precautions must be taken.
  • (D) at least one electrically non-conductive, porous and ion-permeable layer, which is positioned between the cathode (A) and layer (C), and at least one electrically non-conductive, porous and ion-permeable layer between anode (B) and layer (C ) is positioned.
  • the cathode (A) contains at least one lithium-ion-containing transition metal compound, such as the transition metal compounds L1C0O2, LiFeP0 4 or lithium manganese spinel known to those skilled in lithium ion battery technology.
  • the cathode (A) contains, as lithium ion-containing transition metal compound, a lithium ion-containing transition metal oxide which contains manganese as the transition metal.
  • lithium ion-containing transition metal oxides which contain manganese as the transition metal 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 encompassed by 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.
  • manganese can occur in the cathode (A) in the formal oxidation state +4. More preferably, manganese occurs in cathode (A) in a formal oxidation state in the range +3.5 to +4.
  • lithium ion-containing transition metal mixed oxide which contains less than 0.1% by weight of sodium is therefore 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 context of 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 compound is selected from manganese-containing lithium iron phosphates and preferably from manganese-containing spinels and manganese-containing transition metal oxides having a layer structure, in particular manganese-containing transition metal mixed oxides having a layer structure.
  • lithium ion-containing transition metal compound is selected from those compounds having a more than stoichiometric amount of lithium.
  • manganese-containing spinels are selected from those of the general formula (I) wherein the variables are defined as follows: 0.9 ⁇ a ⁇ 1, 3, preferably 0.95 ⁇ a ⁇ 1, 15, 0 ⁇ b ⁇ 0.6, for example 0.0 or 0.5,
  • 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: 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.
  • 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.
  • 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 having 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 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.
  • 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 ⁇ -propylene.
  • 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 have 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.
  • Anodes made of carbon can be selected, for example, from hard carbon, soft carbon, graphene, graphite and in particular graphene. phit, 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.
  • 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.
  • electrochemical cells according to the invention contain (C) at least one layer, also referred to as layer (C), which (a) comprises at least one lithium and oxygen-containing, electrochemically active transition metal compound, also referred to as transition metal compound (a), and (b) optionally at least one Binder, in short also called binder (b) or binder (b) contains.
  • layer (C) which (a) comprises at least one lithium and oxygen-containing, electrochemically active transition metal compound, also referred to as transition metal compound (a), and (b) optionally at least one Binder, in short also called binder (b) or binder (b) contains.
  • transition metal compounds (a) are known as such.
  • the transition metal compounds (a) are those materials which are already used as electrode materials both in the cathode and in the anode in electrochemical cells.
  • the lithium and oxygen-containing, electrochemically active transition metal compound (a) of layer (C) is a particulate material.
  • transition metal compounds (a) can have an average particle diameter (D50) in the range from 0.05 to 100 ⁇ m, preferably from 2 to 50 ⁇ m.
  • the lithium and oxygen-containing, electrochemically active transition metal compound (a) from layer (C) is a compound selected from the group consisting of lithium titanates of the formula Li 4 + x Ti 5 0 2 with x equal to a numerical value of> 0 to 3, lithium iron phosphate, lithium-nickel-cobalt-manganese oxides, lithium-nickel-cobalt-aluminum oxides, lithium manganese oxides and mixtures thereof, in particular a lithium titanate of the formula
  • the lithium and oxygen-containing, electrochemically active transition metal compound (a) from layer (C) is a compound which has a potential difference between 1 and 5 V, preferably between 1 and 5, in an electrochemical cell 4 V, more preferably between 1 and 2.5 V, in particular between 1 and 1, 8 V with respect to Li / Li * .
  • binder (b) is selected from such binders as described in connection with binder for the cathode (s) (A).
  • layer (C) comprises a binder (b) selected from the group of polymers consisting of polyvinyl alcohol, styrene-butadiene rubber, polyacrylonitrile, carboxymethylcellulose and fluorine-containing (co) polymers, in particular selected from styrene-butadiene- Rubber and fluorine-containing (co) polymers.
  • a binder (b) selected from the group of polymers consisting of polyvinyl alcohol, styrene-butadiene rubber, polyacrylonitrile, carboxymethylcellulose and fluorine-containing (co) polymers, in particular selected from styrene-butadiene- Rubber and fluorine-containing (co) polymers.
  • binder (b) and binder for cathode and for anode, if present, are the same.
  • 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) has an average thickness in the range from 0.1 ⁇ m to 250 ⁇ m, preferably from 1 ⁇ m to 50 ⁇ m, and particularly preferably from 9 ⁇ m to 35 ⁇ m.
  • Layer (C) may comprise further constituents in addition to the transition metal compound (a) and the optional binder (b), for example support materials such as fibers or nonwovens, which provide improved stability of layer (C), without their necessary porosity and ion permeability affect.
  • Electrochemical cells according to the invention also contain (D) at least one electrically non-conductive, porous and ion-permeable layer positioned between cathode (A) and layer (C) and at least one electrically nonconductive, porous and ion-permeable layer between anode (B ) and layer (C) is positioned.
  • an electrochemical cell according to the invention contains at least two electrically nonconductive, porous and ion-permeable layers, which in the context of the present invention are also called short layers (D) in the plural or layer (D) in the singular.
  • the layers (D) may be the same or different, with a difference between two layers (D), for example, in their chemical composition or their specific material properties such as density, porosity or spatial dimensions, such as For example, the thickness, may be justified, the list of potential differences is not exhaustive.
  • Electrically non-conductive, porous and ion-permeable layers are known as such and are already used, for example, as simple separators in electrochemical cells between cathode and anode.
  • Layer (D) may be, 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.
  • polyolefin membranes can be composed of one or more layers.
  • Layer (D) is preferably a nonwoven.
  • organic nonwovens 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 nonwovens.
  • PET nonwovens polyethylene terephthalate nonwovens
  • PBT nonwovens polybutylene terephthalate nonwovens
  • polyimide nonwovens polyethylene and polypropylene nonwovens
  • PVdF nonwovens PVdF nonwovens
  • PTFE nonwovens examples of organic nonwovens.
  • inorganic nonwovens examples include glass fiber nonwovens and ceramic fiber nonwovens.
  • the layer (C) or the structural unit consisting of layer (C) and two layers (D) aligned parallel to one another can also be produced as a semifinished product independently of the structure of the electrochemical cell according to the invention and later as a finished separator by a battery manufacturer or part of the separator between the cathode and anode are incorporated in an electrochemical cell
  • Another object of the present invention is therefore also a sheet-like constructed sheet-like separator for the separation of a cathode and an anode in an electrochemical cell containing
  • transition metal compound (a) at least one lithium and oxygen-containing, electrochemically active transition metal compound, called transition metal compound (a) short, and
  • binder (b) optionally at least one binder, called binder (b) for short, and
  • (D) two parallel aligned layers that are electrically nonconductive, porous and ion permeable, abbreviated to layers (D), with layer (C) between the two layers (D).
  • transition metal compound (a) at least one lithium and oxygen-containing, electrochemically active transition metal compound, called transition metal compound (a) short, and
  • binder (b) optionally at least one binder, abbreviated to binder (b), as part of a separator which provides for the separation of a cathode and an anode in an electrochemical cell.
  • the term "sheet-like" means that the described separator, a three-dimensional body, in one of its three spatial dimensions (dimensions), namely the thickness, is smaller than in the other two dimensions, the length and the width.
  • the thickness of the separator is at least a factor of 5, preferably at least a factor of 10, particularly preferably at least a factor of 20 smaller than the second largest extent.
  • Preferred embodiments with respect to layer (C) and the constituents contained therein, namely the transition metal compound (a) and the optionally present binder (b), and with respect to the layers (D) are identical to those described above in connection with the electrochemical cell according to the invention.
  • the separators are sheet-like, they can be installed not only as a flat layers between the cathode and anode, but can also be rolled up depending on the requirements, wound or folded as desired.
  • a sheet-like separator constructed in layers has a thickness in the range from 5 ⁇ m to 250 ⁇ m, preferably from 10 ⁇ m to 50 ⁇ m.
  • the separator according to the invention in the layer (C) as transition metal compound (a) lithium titanate of the formula ⁇ _ ⁇ 4 + ⁇ 5 0 ⁇ 2, wherein x is a numerical value of> 0 to 3, and as binder (b) a styrene-butadiene Rubber or a fluorine-containing (co) polymer, and the two layers (D) are each a non-woven, in particular a non-woven made of an organic polymer.
  • separators having a layer structure (D) / (C) / (D) is known in principle and is described, for example, in WO 2009/033627.
  • the laminar separator constructed in layers according to the invention can be produced, for example, in the form of endless belts, which are further processed by the battery manufacturer, in particular to form an electrochemical cell according to the invention.
  • Inventive electrochemical cells or the separator according to the invention contain in a particularly preferred embodiment as a transition metal compound (a) lithium titanate of the formula Li4 + xTi 5 0i2, wherein x is a numerical value of> 0 to 3.
  • lithium titanate of the formula Li 4 Ti 5 O 2 can be further enriched with lithium, ie, formally reduce the oxidation number of the titanium. This process is called lithiation in the context of the present invention.
  • Lithiation of the lithium titanate of the formula Li 4 Ti 5 O 2 can be carried out before or after Structure of the electrochemical cells according to the invention or of the separator according to the invention take place.
  • Possibilities for lithiation of the lithium titanate of the formula Li 4 Ti 5 O 2 are, for example:
  • Possibility (i) can be realized, for example, by arranging Li 4 Ti 5 O 2 as an electrode in a half cell with lithium as the counterelectrode, and then impressing a current until the potential falls below 1.5 V relative to Li / Li * .
  • a lithium powder such as "SMLP ® " FMC with Li4Ti 5 0i2 be mixed in powder form, or Li4Ti 5 0i2 is coated by gas phase processes such as CVD or PVD with lithium, for example by vapor deposition of lithium for example at 600 ° C in a vacuum.
  • gas phase processes such as CVD or PVD with lithium, for example by vapor deposition of lithium for example at 600 ° C in a vacuum.
  • the Li4Ti 5 Oi2 can also be lithiated by reaction with a lithium alkyl or lithium aryl.
  • a further subject of the present invention is therefore also a process for producing an electrochemical cell as described above, comprising
  • Electrochemical cells according to the invention may further comprise customary constituents, for example conductive salt, nonaqueous solvent, furthermore cable connections and housings.
  • electrochemical cells according to the invention contain at least one non-aqueous solvent, which may be liquid or solid at room temperature, preferably liquid at room temperature, and which is preferably selected from polymers, cyclic or non-cyclic ethers, cyclic or not cyclic acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • non-aqueous solvent which may be liquid or solid at room temperature, preferably liquid at room temperature, and which is preferably selected from polymers, cyclic or non-cyclic ethers, cyclic or not cyclic acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • 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) in which R 1 , R 2 and R 3 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 2 and R 3 are not both tert-butyl.
  • R 1 is methyl and R 2 and R 3 are each hydrogen or R 1 , R 2 and R 3 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (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 , UCIO 4 , LiAsF 6 , L1CF 3 SO 3, LiC (CnF 2n + iSO 2) 3, lithium imides such as LiN (CnF 2 n + iSO 2 ) 2 , where n is an integer in the range of 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:
  • 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.
  • Inventive electrochemical cells provide a high voltage of up to about 4.8 V 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 during 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 electrochemical cells according to the invention as described above in automobiles, electric motor-powered two-wheelers, aircraft, ships or stationary energy storage.
  • Another object of the present invention is therefore also the use of lithium-ion batteries according to the invention in devices, in particular 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, such as computers, especially laptops, phones 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.
  • glass fiber fleece (Whatman, 260 ⁇ 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 two glass fiber fleece discs, each about 130 ⁇ m thick, were formed from a glass fiber fleece disc.
  • Lithium titanate (LTO-2, CHINA ELEMENT INTERNATIONAL LIMITED) was dried for 16 hours at 200 ° C in a vacuum oven. Thereafter, the fine powder was mixed in waxed ratio of 9: 1 with polyvinylidene fluoride commercially available as Kynar FLEX ® 2801 from the company Arkema, and was then added dropwise to N-methyl pyrrolidone, to obtain a viscous paste.. The viscous paste thus obtained was stirred for a period of 16 hours.
  • the resulting paste was stretched evenly over a PET nonwoven, commercially available as fleece "PES20” from APODIS Filtertechnik OHG, and the LTO-coated nonwoven was dried for 2 hours in a drying oven at 120 ° C. After drying, a nonwoven fabric was obtained Approximately 15 mg / cm 2 of LTO coating was then punched out of it with 13 mm diameter disks and dried again in a vacuum drying oven at 120 ° C. for 16 hours to obtain layer C.1.
  • the LTO-coated disc C.1 was transferred to an argon-filled glove box which was sandwiched between two glass fiber fleece discs to obtain separator S.1.
  • Trial 1.1 was repeated, but layer C.1 was placed in a solution of butyllithium in hexane (Aldrich) in an argon-filled glove box for 16 hours to lithiate the LTO, with the originally white layer A.1 becoming uniformly dark. Subsequently, layer C.1 was washed with hexane (anhydrous, Aldrich) and then diethylene carbonate (anhydrous, Aldrich), dried at room temperature for 16 h, to give layer (C.2). Layer C.2 was sandwiched between two glass fiber nonwoven discs to obtain separator S.2.
  • Experiment 1.1 was repeated, but instead of LTO, overlithiated layer oxide Lii, 2Nio, 22Coo, i2Mno, 6602 (BASF) was used to obtain layer C.5 or separator S.5, respectively.
  • overlithiated layer oxide Lii, 2Nio, 22Coo, i2Mno, 6602 (BASF) was used to obtain layer C.5 or separator S.5, respectively.
  • Example 1.1 The experiment of Example 1.1 was repeated under the same conditions, but the PET nonwoven fabric was not coated with LTO but used uncoated to obtain layer C.6 and hence comparative separator V-S.6.
  • Comparative Example I.6 was repeated under the same conditions, but instead of the PET nonwoven (layer C.6), a separator was used, as described in publication WO2004 / 021475, around layer C.7 and consequently comparison separator VS.7 to receive.
  • Experiment 1.1 was repeated in a modified form using lithium powder (Aldrich) instead of LTO, to obtain layer C.8 or comparative separator V-S.8.
  • the PET fleece was coated with the lithium / DOL / Kynarflex dispersion by knife coating in an argon-flooded glove box. Drying was carried out overnight in vacuo at 40 ° C.
  • Cathode (A.1) a lithium-nickel-manganese spinel electrode was used, which was prepared as follows. One mixed with each other:
  • the resulting 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 resulting paste was laced to 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 separator according to the invention (S.1) prepared according to 1.1 was used as a separator and dripped in an argon-filled glove box with electrolyte and positioned between a cathode (A.1) and an anode (B.1), so that both the anode as well as the cathode had direct contact to the separator. Electrolyte was added and the electrochemical cell EZ.1 according to the invention was obtained. Electrochemical testing was between 4.25V and 4.8V in three-electrode Swagelok cells.
  • Example 11 Analogous to Example 11.1, the electrochemical cells EZ.2, EZ.3, EZ.4. Became separators S.2, S.3, S.4, S.5, as well as VS.6, VS.7 and VS.8 , EZ.5, as well as V-EZ.6, V-EZ.7 and V-EZ.8 and tested accordingly.
  • FIG. 1 shows the schematic structure of a disassembled electrochemical cell for testing separators according to the invention and not according to the invention.
  • FIG. 1 The explanations in FIG. 1 mean:
  • the electrochemical cell EZ.1 could be charged and discharged very stably over 150 cycles and lost only 8% of the starting capacity after 130 cycles
  • the electrochemical cell EZ.2 could be charged and discharged very stable over 150 cycles and lost no starting capacity after 130 cycles.
  • the electrochemical cell EZ.3 could be charged and discharged very stably over 150 cycles and lost only 26% of the starting capacity after 130 cycles
  • the electrochemical cell EZ.4 could be charged and discharged very stably over 150 cycles and lost only 15% of the starting capacity after 130 cycles
  • the electrochemical cell EZ.5 could be charged and discharged very stably over 150 cycles and lost only 17% of the starting capacity after 130 cycles
  • the electrochemical cells V-EZ.6 from the comparative example degraded relatively strongly and lost 42% of the starting capacity after about 130 cycles.
  • the electrochemical cells V-EZ.7 from the comparative example degraded relatively strongly and lost 41% of the starting capacity after about 130 cycles.
  • the electrochemical cell V-EZ.8 from the comparative example could be charged and discharged very stably over 150 cycles and lost only about 4% of the starting capacity after 130 cycles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne des cellules électrochimiques contenant : (A) au moins une cathode contenant au moins un composé de métal de transition contenant des ions lithium; (B) au moins une anode; (C) au moins une couche contenant (a) au moins un composé de métal de transition électrochimiquement actif contenant du lithium et de l'oxygène, et (b) éventuellement au moins un liant; et (D) au moins une couche non électroconductrice, poreuse et perméable aux ions, qui est positionnée entre la cathode (A) et la couche (C), ainsi qu'au moins une couche non électroconductrice, poreuse et perméable aux ions, qui est positionnée entre l'anode (B) et la couche (C). La présente invention concerne en outre l'utilisation de cellules électrochimiques selon la présente invention, leur production ainsi qu'un séparateur spécial pour la séparation d'une cathode et d'une anode dans une cellule électrochimique.
EP12822507.5A 2011-08-08 2012-07-19 Cellules électrochimiques Withdrawn EP2742552A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12822507.5A EP2742552A4 (fr) 2011-08-08 2012-07-19 Cellules électrochimiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11176823 2011-08-08
EP12822507.5A EP2742552A4 (fr) 2011-08-08 2012-07-19 Cellules électrochimiques
PCT/IB2012/053671 WO2013021299A1 (fr) 2011-08-08 2012-07-19 Cellules électrochimiques

Publications (2)

Publication Number Publication Date
EP2742552A1 true EP2742552A1 (fr) 2014-06-18
EP2742552A4 EP2742552A4 (fr) 2015-05-06

Family

ID=47667940

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12822507.5A Withdrawn EP2742552A4 (fr) 2011-08-08 2012-07-19 Cellules électrochimiques

Country Status (5)

Country Link
EP (1) EP2742552A4 (fr)
JP (1) JP5686928B2 (fr)
KR (1) KR20140064845A (fr)
CN (1) CN103718339A (fr)
WO (1) WO2013021299A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013136223A1 (fr) * 2012-03-14 2013-09-19 Basf Se Matériaux composites, leur fabrication et leur utilisation dans des cellules électrochimiques
CN106558664A (zh) * 2015-09-25 2017-04-05 比亚迪股份有限公司 一种锂离子电池用隔膜及其制备方法以及锂离子电池
JP7053192B2 (ja) * 2017-08-30 2022-04-12 旭化成株式会社 非水電解質電池用吸着層並びにこれを用いた非水電解質電池用セパレータ及び非水電解質電池
CN112219299B (zh) * 2018-05-15 2024-06-25 魁北克电力公司 用于锂离子电池组的纤维素基自支撑膜
KR102331720B1 (ko) 2019-02-18 2021-11-26 삼성에스디아이 주식회사 분리막 및 이를 채용한 리튬전지
CN115679122B (zh) * 2022-11-23 2024-03-15 陈畅 一种复合结构的电极及其制作方法与应用

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6427959U (fr) * 1987-08-12 1989-02-17
JPH07282838A (ja) * 1994-04-13 1995-10-27 Shin Kobe Electric Mach Co Ltd 密閉形鉛蓄電池
CN1168543A (zh) * 1996-05-29 1997-12-24 叶顺纪 蓄电池用硅玻复合隔板
US6379840B2 (en) * 1998-03-18 2002-04-30 Ngk Insulators, Ltd. Lithium secondary battery
JP2003132951A (ja) * 2001-10-25 2003-05-09 Matsushita Electric Ind Co Ltd リチウムポリマー二次電池の製造方法
TWI330136B (en) * 2005-11-28 2010-09-11 Lg Chemical Ltd Organic/inorganic composite porous membrane and electrochemical device using the same
TWI368347B (en) * 2006-02-16 2012-07-11 Lg Chemical Ltd Electrode including organic/inorganic composite coating layer and electrochemical device prepared thereby
JP5137312B2 (ja) * 2006-03-17 2013-02-06 三洋電機株式会社 非水電解質電池
DE102006021273A1 (de) * 2006-05-05 2007-11-08 Carl Freudenberg Kg Separator zur Anordnung in Batterien und Batterie
WO2008039417A1 (fr) * 2006-09-25 2008-04-03 Zpower Inc. Séparateur résistant à l'oxydation destiné à des accumulateurs alcalins
JP5087383B2 (ja) * 2007-12-11 2012-12-05 三星エスディアイ株式会社 非水系リチウム二次電池用セパレータ
EP2639855A3 (fr) * 2008-03-27 2013-12-25 ZPower, LLC Séparateur d'électrode
DE102009018804A1 (de) * 2009-04-24 2010-10-28 Li-Tec Battery Gmbh Elektrochemische Zelle mit Lithiumtitanat
HUE066432T2 (hu) * 2009-09-29 2024-08-28 Lg Energy Solution Ltd Szeparátor és az azt tartalmazó elektrokémiai berendezés
KR101093916B1 (ko) * 2009-12-15 2011-12-13 삼성에스디아이 주식회사 세퍼레이터, 그 제조방법 및 리튬 이차전지
CN102117905B (zh) * 2009-12-30 2014-01-29 上海比亚迪有限公司 一种复合隔膜及其制备方法及电池
DE102010030197A1 (de) * 2010-06-17 2011-12-22 Sb Limotive Company Ltd. Lithium-Ionen-Zelle

Also Published As

Publication number Publication date
JP5686928B2 (ja) 2015-03-18
JP2014527266A (ja) 2014-10-09
CN103718339A (zh) 2014-04-09
KR20140064845A (ko) 2014-05-28
EP2742552A4 (fr) 2015-05-06
WO2013021299A1 (fr) 2013-02-14

Similar Documents

Publication Publication Date Title
EP2994424B1 (fr) Particule sphérique, sa fabrication et son utilisation
KR101983099B1 (ko) 이차전지용 양극활물질, 이를 포함하는 이차전지용 양극 및 이차전지
JP6609644B2 (ja) コバルト酸リチウムを合成するための正極活物質を含むリチウム二次電池、この製造方法
EP2994425B1 (fr) Particule sphérique, sa fabrication et son utilisation
EP2742552A1 (fr) Cellules électrochimiques
KR20210112325A (ko) 전극 활물질의 제조 방법
EP2814778B1 (fr) Particules, procédé de production desdites particules et utilisation desdites particules
CN105742563A (zh) 非水电解质二次电池
KR20210036869A (ko) Li 및 Mn 기반의 플루오르화 산화물
CN114341059A (zh) 作为钠离子电池阴极材料的钠层状氧化物及其制造方法
JP2023015188A (ja) 非水電解質二次電池用正極活物質の製造方法
EP3215462A1 (fr) Oxyde mixte de métaux de transition pour batteries à ions lithium
WO2013127737A1 (fr) Séparateurs pour cellules électrochimiques contenant des particules polymères
WO2012038269A1 (fr) Procédé de fabrication de matériaux d'électrodes
EP2619139B1 (fr) Procede de preparation de materiaux d'electrode
EP2789031A1 (fr) Cellules électrochimiques contenant un polymère renfermant de l'azote
JP6403943B2 (ja) リチウムイオン二次電池、及び、その製造方法、並びに、その使用方法
WO2013102533A1 (fr) Matériaux, production et utilisation desdits matériaux
US20130040183A1 (en) Electrochemical cells
EP2548244A1 (fr) Matériau d'électrode et son utilisation pour la fabrication de cellules électrochimiques
WO2013144842A1 (fr) Cellule électrochimique contenant un polymère à base de soufre
EP2695222A2 (fr) Cellules électrochimiques qui contiennent des échangeurs d'ions
WO2011144605A1 (fr) Composés et leur utilisation pour produire des piles électrochimiques
WO2013084098A1 (fr) Cellules électrochimiques contenant des ligands chélatés
EP4229693A1 (fr) Procédé de fabrication de matériau actif de cathode revêtu

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140310

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: GARSUCH, ARND

Inventor name: SCHULZ-DOBRICK, MARTIN

Inventor name: LEITNER, KLAUS

Inventor name: GRONWALD, OLIVER

RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150410

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 2/16 20060101AFI20150405BHEP

Ipc: H01M 10/0525 20100101ALI20150405BHEP

Ipc: H01M 10/052 20100101ALI20150405BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 2/16 20060101AFI20151125BHEP

Ipc: H01M 10/052 20100101ALI20151125BHEP

Ipc: H01M 10/0525 20100101ALI20151125BHEP

INTG Intention to grant announced

Effective date: 20151221

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160503