EP2820693A1 - Séparateurs pour cellules électrochimiques contenant des particules polymères - Google Patents

Séparateurs pour cellules électrochimiques contenant des particules polymères

Info

Publication number
EP2820693A1
EP2820693A1 EP13705804.6A EP13705804A EP2820693A1 EP 2820693 A1 EP2820693 A1 EP 2820693A1 EP 13705804 A EP13705804 A EP 13705804A EP 2820693 A1 EP2820693 A1 EP 2820693A1
Authority
EP
European Patent Office
Prior art keywords
particles
layer
separator
separator according
polyvinylpyrrolidone
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Withdrawn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
EP13705804.6A
Other languages
German (de)
English (en)
Inventor
Oliver Gronwald
Klaus Leitner
Nicole Janssen
Christoph J. Weber
Michael Roth
Gunter Hauber
Sandra Falusi
Sigrid Geiger
Margitta Berg
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
Carl Freudenberg KG
Original Assignee
BASF SE
Carl Freudenberg KG
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, Carl Freudenberg KG filed Critical BASF SE
Priority to EP13705804.6A priority Critical patent/EP2820693A1/fr
Publication of EP2820693A1 publication Critical patent/EP2820693A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • 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
    • H01M50/449—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
    • H01M50/463—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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H01M2200/20—Pressure-sensitive devices
    • 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
    • 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
    • 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
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to separators for electrochemical cells, comprising
  • the present invention relates to the use of separators according to the invention, as well as devices, in particular electrochemical cells, containing separators according to the invention.
  • Saving energy has long been an object of growing interest.
  • Electrochemical cells such as 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.
  • separators In electrochemical cells, the positively and negatively charged electrode masses are mechanically separated from one another by nonelectrically conductive layers, so-called separators, to avoid an internal discharge. Due to their porous structure, these separators allow the transport of ionic charges as a basic requirement for the current
  • separators Current drain during battery operation. Basic requirements for separators consist in the chemical and electrochemical stability compared to the active electrode materials and the electrolyte. In addition, a high mechanical strength must be given in relation to the tensile forces occurring during the battery cell manufacturing process. At a structural level, high porosity is required to absorb the electrolyte to ensure high ionic conductivity. At the same time, pore size and the structure of the channels must effectively suppress the growth of metal dendrites to avoid shorting, as described in Journal Power Sources 2007, 164, 351-364. Separators as microporous layers often consist of either a polymer membrane or a nonwoven fabric.
  • polymer membranes based on polyethylene and polypropylene are commonly used as separators in electrochemical cells, which membranes show a lack of resistance at elevated temperatures of 130 to 150 ° C.
  • An alternative to the frequently used polyolefin separators are separators based on nonwovens, which are filled with ceramic particles and additionally fixed with an inorganic binder of oxides of the elements silicon, aluminum and / or zirconium, as in DE10255122 A1, DE10238941 A1, DE10208280 A1, DE10208277 A1 and WO 2005/038959 A1.
  • the nonwovens filled with ceramic particles have increased surface weights and greater thicknesses in comparison with the unfilled nonwovens.
  • 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. Such separators are intended to avoid short circuits caused by metal dendrites. In WO 2009/033627, however, no long-term cyclization experiments are disclosed.
  • WO 2009/103537 discloses a sheet having a base body having pores, the sheet further comprising a binder which is crosslinked. In a preferred embodiment, the main body is at least partially filled with particles.
  • the disclosed layers can be used as separators in batteries. In WO 2009/103537, however, no electrochemical cells are produced and investigated with the layers described.
  • WO 2010/1 18822 discloses an unbalanced battery separator having a cathode side and an anode side which differ in their respective material consistency.
  • the separators known from the literature have with regard to one or more of the desired properties for the separators such as low thickness, low basis weight, good mechanical stability during processing, for. As high flexibility or low abrasion, or in battery operation against metal dendrite growth, good temperature resistance, low shrinkage behavior, high porosity, good ion conductivity and good wettability with the electrolyte liquids, still deficits. Finally, some of the deficiencies of the separators are responsible for a reduced lifetime of the electrochemical cells containing them. Furthermore, separators must in principle be not only mechanically but also chemically stable with respect to the cathode materials, the anode materials and the electrolyte.
  • (c) optionally a basic body, wherein the mass ratio of the crosslinked polyvinylpyrrolidone in the form of particles (a) to the sum of the mass of the binder (b) in the layer (A) has a value in the range of 99.9: 0.1 to 50:50.
  • the separator which is suitable for an electrochemical cell, in particular a rechargeable electrochemical cell, comprises at least one layer, also called layer (A) for short, which comprises (a) crosslinked polyvinylpyrrolidone in the form of particles, in short also particles of crosslinked one!
  • Crosslinked polyvinylpyrrolidone in the form of particles is known in principle.
  • Crosslinked polyvinylpyrrolidone which is also referred to as crospovidone, is a water-insoluble but swellable polymer of vinylpyrrolidone which has been used, for example, in a so-called popcorn polymerization, for example in US Pat. No. 3,933,766 or WO 2007/071580, page 2, lines 21 to Page 5, line 33 described can be produced.
  • the crosslinked polyvinylpyrrolidone usually consists of more than 80 wt .-%, preferably more than 90 wt .-%, in particular more than 96 wt .-% of the monomer vinylpyrrolidone.
  • Powders of crosslinked polyvinylpyrrolidone having different average particle sizes can be produced in a wide range either by the production process itself or by comminution of the polymer particles occurring in the preparation of crosslinked polyvinylpyrrolidone and suitable screening processes.
  • suitable screening processes for pharmaceutical applications, for example as a tablet disintegrant product types with different areas of the average particle size are commercially available, for example under the product name Kollidon ® of BASF SE.
  • the crosslinked polyvinylpyrrolidone in the form of particles (a) in layer (A) preferably has an average particle size in the range from 0.01 to 50 ⁇ m, preferably in the range from 0.01 to 10 ⁇ m, in particular in the range from 0.1 to 5 ⁇ on.
  • the separator for an electrochemical cell according to the invention is characterized in that the crosslinked polyvinylpyrrolidone contained in layer (A) in the form of particles (a) has an average particle size in the range from 0.1 to 5 ⁇ m.
  • the particle size distribution was determined by means of laser diffraction technology in powder form in accordance with DIN ISO 13320-1 using a mastersizer from Malvern Instruments GmbH,dorfberg, Germany.
  • the decisive value for the mean particle size is the so-called d90 value.
  • the d90 value of the volume-weighted distribution is the particle size for which 90% of the particle volume of particles is less than or equal to the d90 value.
  • the particles of crosslinked polyvinylpyrrolidone (a) can be shaped differently depending on the manufacturing process. In principle, regularly shaped particles, for example spherical or irregularly shaped particles are conceivable. Irregularly shaped particles of crosslinked polyvinylpyrrolidone can be obtained, for example, by the above-described popcorn polymerization.
  • the particles which are preferably irregularly shaped in the context of the present invention are polyhedral bodies which have both outwardly curved and inwardly curved outer surface portions.
  • V. Buehler "Polyvinylpyrrolidone Excipients for Pharmaceuticals", p. 130, Springer Verlag Berlin Heidelberg, 2005.
  • the separator for an electrochemical cell according to the invention is characterized in that the particles of crosslinked polyvinylpyrrolidone (a) containing layer (A) have an irregular shape.
  • the inventive separator for an electrochemical cell is characterized in that the crosslinked polyvinylpyrrolidone contained in layer (A) in the form of particles (a) has an average particle size in the range of 0.1 to 5 ⁇ and the particles have an irregular shape.
  • the proportion by weight of the crosslinked polyvinylpyrrolidone in the form of particles (a) on the total weight of the layer (A) can be up to 99.9% by weight.
  • the proportion by weight of the crosslinked polyvinylpyrrolidone in the form of particles (a) in the total mass of layer (C) is preferably at least 5% by weight, more preferably the weight fraction is from 20 to 80% by weight, in particular from 30 to 60% by weight. -%.
  • Layer (A) of the electrochemical cell separator according to the invention contains at least one binder (b), for example one or more organic polymers. Suitable binders are, for example, organic (co) polymers, as for example in WO
  • Suitable (co) polymers 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 selected 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 have polymerized at least 50 mol% of propylene 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.
  • binders are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyvinylpyrrolidone, polyimides and polyvinyl alcohol.
  • PEO polyethylene oxide
  • 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, perfluoroalkylvinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • Suitable binders are in particular polyvinyl alcohol, water-soluble polyvinylpyrrolidone, styrene-butadiene rubber, polyacrylonitrile, carboxymethylcellulose and fluorine-containing
  • (Co) polymers in particular styrene-butadiene rubber.
  • the separator for an electrochemical cell according to the invention is characterized in that the binder (b) contained in layer (A) is selected from the group of polymers consisting of polyvinyl alcohol, water-soluble polyvinylpyrrolidone, styrene-butadiene Rubber, polyacrylonitrile, carboxymethylcellulose and fluorine-containing (co) polymers, in particular water-soluble polyvinylpyrrolidone and styrene-butadiene rubber.
  • Layer (A) is further characterized in that the mass ratio of the crosslinked polyvinylpyrrolidone in the form of particles (a) to the sum of the mass of the binder (b) in the layer (A) has a value in the range of 99.9: 0.1 to 50: 50, preferably in the range from 99: 1 to 80: 20, particularly preferably in the range from 98: 2 to 90: 10, in particular in the range from 97: 3 to 93: 7.
  • Layer (A) may comprise, in addition to the crosslinked polyvinylpyrrolidone in the form of particles (a) and the at least one binder (b) as a further constituent, a base body, for example a base body (c) consisting of fibers, such as a fabric, a felt, a nonwoven , a paper or a mat, in particular a nonwoven, wherein the base body (c) provides improved stability of layer (A) without impairing its necessary porosity and ion permeability.
  • layer (A) as the main body may also contain at least one porous plastic layer, for example a polyolefin membrane. ran, in particular a polyethylene or a polypropylene membrane.
  • polyolefin membranes can be composed of one or more layers. Porous polyolefin membranes or nonwovens themselves can fulfill the function of a separator as explained above.
  • layer (A) may additionally also contain inorganic particles, as mentioned, for example, in WO 2009/033627, page 18, lines 4 to 8.
  • the separator according to the invention contains less than 5 wt .-%, in particular less than 1 wt .-% of inorganic particles based on the total mass of the separator.
  • layer (A) may in principle also contain particles of other organic polymers, as mentioned for example in WO 2009/033627, page 12, line 23 to page 17, line 18.
  • the separator according to the invention preferably contains less than 50% by weight, more preferably less than 20% by weight, very preferably less than 5% by weight, in particular less than 1% by weight % Of particles of other organic polymers based on the total mass of the particles present in layer (A).
  • the separator for an electrochemical cell according to the invention is characterized in that layer (A) further comprises a base body (c) consisting of fibers, in particular that layer (A) further comprises a base body (c) made of nonwoven fabric.
  • the main body (c) of nonwoven fabric can be made of inorganic or organic materials, preferably organic materials.
  • 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 separator for an electrochemical cell according to the invention is characterized in that the base body (c) consists of fibers and has first pores formed by the fibers, wherein the base body (c) is at least partially crosslinked with particles of Polyvinylpyrrolidone (a) is filled and wherein the particles of crosslinked polyvinylpyrrolidone (a) at least partially fill the first pores and formed with particles of crosslinked polyvinylpyrrolidone (a) filled areas, wherein the particles of crosslinked polyvinylpyrrolidone (a) in the filled areas second pores wherein the average diameter of the cross-linked polyvinylpyrrolidone particles (a) is greater than the average pore size of the plurality of second pores.
  • the particles (a) are applied so that they are distributed homogeneously in the body (c).
  • the separator according to the invention for an electrochemical cell is characterized in that the particles of crosslinked polyvinylpyrrolidone (a) contained in layer (A) are homogeneously distributed in the main body (c) in a planar manner.
  • the main body (c) may also have a coating of the particles (a).
  • a coating also advantageously effects the suppression of short circuits in electrochemical cells.
  • the boundary region between coating and main body (c) is necessarily at least partially filled with particles.
  • the separator for an electrochemical cell according to the invention is characterized in that at least part of the filled regions is formed as a coating of the base body (c) with the particles of crosslinked polyvinylpyrrolidone (a).
  • a base body (c) made of nonwoven fabric is preferably used, wherein the fibers from which the nonwoven fabric is produced are preferably made of at least one, in particular an organic polymer selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polyacrylonitrile, Polyvinylidene fluoride, polyetheretherketone, polyethylene naphthalate, polysulfone, polyimide, polyester, polypropylene, polyoxymethylene, polyamide and polyvinylpyrrolidone.
  • an organic polymer selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate, polyacrylonitrile, Polyvinylidene fluoride, polyetheretherketone, polyethylene naphthalate, polysulfone, polyimide, polyester, polypropylene, polyoxymethylene, polyamide and polyvinylpyrrolidone.
  • nonwovens whose fibers consist of more than 90% by weight, more preferably more than 95% by weight, in particular more than 98% by weight, of polyethylene terephthalate.
  • the separator for an electrochemical cell according to the invention is characterized in that the base body (c) is a nonwoven fabric whose fibers are made of at least one organic polymer selected from the group of polybutylene terephthalate, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyetheretherketone, polyethylene naphthalate, polysulfone, polyimide, polyester, polypropylene, polyoxymethylene, polyamide and polyvinylpyrrolidone.
  • Particular preference is given to nonwovens of polyesters, such as polyethylene terephthalate or polybutylene terephthalate, in particular polyethylene terephthalate.
  • the average length of the fibers of the nonwoven fabric could exceed their average diameter by at least twice, preferably a multiple. As a result of this specific design, a particularly tear-resistant nonwoven fabric can be produced since the fibers can be entangled with one another.
  • At least 90% of the fibers of the nonwoven fabric could have an average diameter of at most 12 ⁇ .
  • This specific embodiment allows the construction of a layer with relatively small pore sizes of the first pores.
  • An even finer porosity can be achieved by virtue of the fact that at least 40% of the fibers of the nonwoven fabric have an average diameter of at most 8 ⁇ m.
  • Layer (A) and in particular the separator as a whole preferably have a thickness of at most 100 ⁇ m.
  • a layer or a separator of this thickness can be easily wound up and allows a very safe battery operation. More preferably, the thickness could be at most 25 ⁇ .
  • a layer or separator with such a thickness allows the construction of very compact batteries or capacitors.
  • the thickness is at least 3, 5 or 10 ⁇ , more preferably between 5 and 100 or between 10 and 60 ⁇ , in particular in the range of 9 to 50 ⁇ .
  • the separator for an electrochemical cell according to the invention is characterized in that layer (A) has an average thickness in the range from 9 to 50 ⁇ m.
  • the separator according to the invention in particular the separator comprising a base body (c) of nonwoven fabric, could have a porosity of at least 25%. Due to its material density, a separator of this porosity particularly effectively suppresses the formation of short circuits. Preferably, the separator could have a porosity of at least 35%. By means of a separator of this porosity, a battery with a high power density can be produced.
  • the non-woven fabric-containing separator described here nevertheless shows very small second pores at high porosity, so that no dendritic progressions can form from one side to the other side of the separator.
  • the second pores form a labyrinth-like structure in which no dendrite-like growths can form from one side to the other side of the separator.
  • the porosity is between 25 and 70, in particular between 35 and 60%.
  • the separator according to the invention in particular of the separator comprising a base body (c) of nonwoven fabric, could have pore sizes of at most 3 ⁇ m.
  • the selection of this pore size has proven to be particularly advantageous to avoid short circuits.
  • Particularly preferred, the pore sizes could be at most 1 ⁇ .
  • Such a separator avoids particularly advantageous short circuits by metal dendrite growth, by abrasion from electrode particles and by direct contact of the electrodes when pressurized.
  • the separator according to the invention in particular the separator comprising a non-woven fabric main body (c), could have a maximum tensile force in the longitudinal direction of at least
  • a separator of this strength can be particularly easily wound on the electrodes of a battery without tearing.
  • the basis weight of the separator according to the invention could be between 10 and 60, in particular between 15 and 50 g / m 2 .
  • a process for the production of the separator according to the invention, in particular of the separator (c) comprising a non-woven fabric-containing separator, is described, for example, in WO
  • the unspecified particles (3) are crosslinked by particles! Polyvinylpyrrolidone (a) as described above, while the remaining components can be used as described.
  • the coating and aftertreatment processes in particular the calendering process highlighted in WO 2009/033627, can be carried out as described there.
  • the separator according to the invention can be mechanically consolidated.
  • the calendering causes a reduction of the surface roughness.
  • the particles (a) present on the surface of the nonwoven fabric show flattening after calendering
  • the separator according to the invention is particularly suitable for the construction of long-lived electrochemical cells with high power and energy density. It shows good mechanical properties at low thickness and low basis weight and has a high porosity and good ion conductivity.
  • the above-described separator for an electrochemical cell according to the invention can be used in batteries, in particular rechargeable batteries, or in capacitors, in order to prevent in particular effectively short circuits.
  • the separator according to the invention can also be used in fuel cells as a gas diffusion layer or membrane since it exhibits good wetting properties and can transport liquids.
  • Another object of the present invention is therefore also the use of the above-described separator according to the invention as a separator in fuel cells, batteries or capacitors, or as a gas diffusion layer or as a membrane.
  • a fuel cell a battery or a condenser, comprising at least one separator according to the invention, as described above.
  • a battery or a condenser comprising at least one separator according to the invention, as described above.
  • the electrochemical cell according to the invention in particular a rechargeable electrochemical cell, is preferably one in which charge transport within the cell is decisively effected by lithium cations.
  • suitable cathode materials suitable anode materials, suitable electrolytes and possible arrangements
  • Particularly suitable cathodes (B) are cathodes in which the
  • Cathode Material Lithium Transition Metal Oxide e.g. As lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide, lithium-manganese oxide (spinel), lithium-nickel-cobalt
  • Alumina lithium nickel cobalt manganese oxide or lithium vanadium oxide, or a lithium transition metal phosphate such as lithium iron phosphate.
  • a lithium transition metal phosphate such as lithium iron phosphate.
  • the separators according to the invention are particularly suitable for such electrochemical cells in which the cathode (B) at least one lithium ion containing transition metal compound, such as those skilled in the lithium-ion battery technology well- known transition metal compounds UC0O2, LiFeP0 4 or contains lithium manganese spinel.
  • the cathode (B) at least one lithium ion containing transition metal compound, such as those skilled in the lithium-ion battery technology well- known transition metal compounds UC0O2, LiFeP0 4 or contains lithium manganese spinel.
  • the cathode (B) preferably contains as lithium ion-containing transition metal compound, a lithium ion-containing transition metal oxide containing 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.
  • those 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.
  • manganese can occur in the cathode (B) in the formal oxidation state +4. More preferably, manganese occurs in cathode (B) in a formal oxidation state in the range +3.5 to +4.
  • 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 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) where the variables are defined as follows:
  • 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 are selected from 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.
  • 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 (B) may contain one or more ingredients.
  • cathode (B) 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 (B) may contain one or more binders, also called binders, for example one or more organic polymers.
  • Suitable binders can be selected, for example, from those binders which are described in connection with the binder (b) for the separator according to the invention.
  • Particularly suitable binders for the cathode (B) 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 (B) can have further conventional components, for example a current conductor, which can be designed in the form of a metal wire, metal grid, metal mesh, expanded metal, metal sheet or a metal foil.
  • a current conductor which can be designed 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 (B) has a thickness in the range of 25 to 200 ⁇ , preferably from 30 to 100 ⁇ , based on the thickness without Stromableiter.
  • the electrochemical cell according to the invention also contains at least one anode (C).
  • anode (C) may be made of carbon anodes, anodes containing Sn or Si, and anodes, the lithium titanate of formula
  • 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 composite materials and Si-metal or Sn metal alloys.
  • the electrochemical cell according to the invention is characterized in that anode (C) is selected from anodes of carbon, anodes containing Sn or Si, and anodes, the lithium titanate of formula Li4 + xTi 5 0i2 with x being equal a numerical value of> 0 to 3.
  • anode (C) is selected from anodes of carbon, anodes containing Sn or Si, and anodes, the lithium titanate of formula Li4 + xTi 5 0i2 with x being equal a numerical value of> 0 to 3.
  • Anode (C) may comprise one or more binders.
  • anode (C) may comprise 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.
  • copper foils are suitable as metal foils.
  • anode (C) 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 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 non-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 non-cyclic acetals, cyclic or non-cyclic organic carbonates and ionic liquids.
  • 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 preferably 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 (s) are preferably used in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, determinable for example by Karl Fischer titration.
  • Inventive electrochemical cells also contain at least one conductive salt. Suitable conductive salts are in particular lithium salts.
  • lithium salts examples include LiPF 6, LiBF 4, UCIO4, LiAsFe, L1CF3SO3, 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 SiF 6, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + i SO 2) m X Li, wherein m is defined as follows:
  • Preferred conductive salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 , LiCl 4 , and particularly preferred are LiPF 6 and LiN (CF 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.
  • electrochemical cells according to the invention have the shape of a prism.
  • 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 ones that you move yourself, such as computers, especially laptops, phones or electrical
  • Hand tools for example from the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • lithium-ion batteries according to the invention containing separator according to the invention, in devices offers the advantage of a longer running time before recharging, a lower capacity loss with longer term and a reduced risk of self-discharge and destruction of the cell caused by short circuit. 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 determination of the particle size distribution was carried out by means of laser diffraction technology in powder form with a mastersizer from Malvern Instruments GmbH,dorfberg, Germany.
  • the average pore size was determined according to ASTME E 1294 (Test Method for Pore Size Characteristics of Membrane Filters Using an Automated Liquid Porosity Meter).
  • Thicknesses were measured with a Precision Thickness Gauge Model 2000 U / Electrics. The measuring area was 2 cm 2 , the measuring pressure 1000 cN / cm 2 .
  • the porosity was calculated from the thickness, weight and densities of the materials used.
  • 100 ⁇ 100 mm samples were punched out and stored for 10 minutes at 160 ° C. in a Labdryer from Mathis. Subsequently, the shrinkage of the patterns was determined.
  • the through-plane air permeability test of the battery separators was determined by the Gurley method (ISO 5636/5).
  • a 15 cm wide PET nonwoven fabric (thickness: 20 ⁇ m, basis weight: 10.6 g / m 2 ) was continuously coated by means of a roll coating method with the above dispersion and dried at 120 ° C.
  • a PET nonwoven fabric (thickness: 19 ⁇ m, basis weight: 11 g / m 2 ) was continuously coated by means of a roll coating method with the above dispersion and dried freely with infrared radiators.
  • V-S.3 Preparation of a Separator Not According to the Invention (V-S.3) To 322 parts of a 1% CMC (carboxymethylcellulose) solution were added 1470 parts of a 65% aluminum oxide dispersion (Al 2 O 3) (average particle size 0.59 ⁇ m) and stirred for 30 minutes. Then, 100 parts of a 50% NBR dispersion (average particle size 0.2 ⁇ ), also added with stirring. The dispersion was stirred for 2 hours and tested for stability for at least 24 hours. The viscosity of the dispersion obtained was 110 cP and had a pH of 9.6.
  • Al 2 O 3 aluminum oxide dispersion
  • a 15 cm wide PET nonwoven fabric (thickness: 19 ⁇ , basis weight: 1 1 g / m 2 ) was continuously coated by means of a roll coating process with the above dispersion and dried at 120 ° C.
  • Pouch cells are electrochemical cells known to those skilled in the art. These each contain a combination of positive and negative electrode, separated by an electrolyte-impregnated separator, which combination is laminated with a metal-polymer composite film.
  • Cathodes of the dimension 5 ⁇ 5 cm and anodes of the dimension 5.6 ⁇ 5.6 cm consisting of the following components were used: Anode: graphite-based anode on copper foil conductor (capacity 1, 7 mAh / cm 2 );
  • a suspension of 91% by weight of graphite powder, 6% by weight of PVDF binder and 3% by weight of conductive carbon black in N-ethylpyrrolidone was initially produced and mixed by means of a planetary mixer.
  • the suspension was applied to the copper carrier film with a Labcoater (Erichsen) and then dried at 120 ° C. in vacuo overnight.
  • Cathode nickel cobalt aluminate cathode on aluminum drain (capacity 1, 4 mAh / cm 2 , LiNio.80 Coo.15Alo.05O2);
  • Electrolyte 1 M LiPF6 dissolved in ethylene carbonate and ethyl methyl carbonate in a mass ratio
  • the electrochemical cell EZ.1 according to the invention was produced from the separator S.1 according to the invention and the comparative electrochemical cell V-EZ.2 was produced from the comparative separator V-S.2.
  • the inventive electrochemical cell EZ.1 was distinguished from the comparative electrochemical cell V-EZ.2 by a higher capacity of 177 mAh / g compared to 159 mAh / g at 0.5 C (Table 1). Furthermore, the cell resistance of V-EZ.2 was at least a factor of 1.4 higher than the cell resistance of EZ.1. In addition, cell EZ.1 according to the invention had significantly better C-rate stability (Table 1). At a load of 2 C, the capacity of V-EZ.2 fell to 9 mAh / g compared to 141 mAh / g of EZ.1. At 4 C, EZ.1 still showed 95 mAh / g while V-EZ.2 did not deliver any more power.

Abstract

La présente invention concerne des séparateurs pour cellules électrochimiques comportant (A) au moins une couche contenant (a) du polyvinylpyrrolidone réticulé sous forme de particules, (b) au moins un liant, et (c) éventuellement un corps de base, le rapport massique du polyvinylpyrrolidone réticulé sous forme de particules (a) par rapport à la somme de la masse du liant (b) dans la couche (A) étant situé dans la plage comprise entre 99,9 : 0,1 à 50 / 50. La présente invention concerne également l'utilisation de séparateurs selon l'invention, et des dispositifs, en particulier des cellules électrochimiques contenant des séparateurs selon l'invention.
EP13705804.6A 2012-02-27 2013-02-25 Séparateurs pour cellules électrochimiques contenant des particules polymères Withdrawn EP2820693A1 (fr)

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CN104137301A (zh) 2014-11-05
KR20140134297A (ko) 2014-11-21
WO2013127737A1 (fr) 2013-09-06

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