EP2807209A1 - Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques - Google Patents

Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques

Info

Publication number
EP2807209A1
EP2807209A1 EP12866500.7A EP12866500A EP2807209A1 EP 2807209 A1 EP2807209 A1 EP 2807209A1 EP 12866500 A EP12866500 A EP 12866500A EP 2807209 A1 EP2807209 A1 EP 2807209A1
Authority
EP
European Patent Office
Prior art keywords
polyether
radical
monomer unit
monomer
metal
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Withdrawn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
EP12866500.7A
Other languages
German (de)
English (en)
Other versions
EP2807209A4 (fr
Inventor
Nicole Janssen
Arno Lange
Helmut MÖHWALD
Oliver Gronwald
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 EP12866500.7A priority Critical patent/EP2807209A4/fr
Publication of EP2807209A1 publication Critical patent/EP2807209A1/fr
Publication of EP2807209A4 publication Critical patent/EP2807209A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide 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
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • 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
    • 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
    • H01M50/489—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
    • 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

Definitions

  • the present invention relates to a novel composite material comprising at least one base body of nonwoven fabric as component (A), at least one nanocomposite material as component (B), at least one polyether or at least one polyether-containing radical as component (C) and optionally a lithium salt as component (D).
  • the invention also relates to a process for the preparation of the new composite material, its use in separators for electrochemical cells and special starting compounds which can be used for the production of nanocomposite material (B).
  • Electro-chemical cells for example batteries or accumulators, can serve 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.
  • lithium-ion secondary batteries having a carbon anode and a metal oxide-based cathode are limited in their energy density. New dimensions in energy density were opened by lithium-sulfur cells.
  • sulfur in the sulfur cathode is reduced via polysulfide ions to S 2_ , which are oxidized again during charging of the cell to form sulfur-sulfur bonds.
  • 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 enable the transport of ionic charges as a basic requirement for the ongoing 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, there must be a high mechanical load capacity compared with the tensile forces occurring during the battery cell production 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 exhibit 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 base 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 201/000858 describes a porous film material comprising at least one carbon-containing Halbmetalloxidphase and can be used as a separator in rechargeable lithium-ion cells. The carbonaceous semimetal oxide phase is obtained by a so-called twin polymerization described by S. Spange et al. in Angew. Chem. Int Ed., 46 (2007) 628-632.
  • 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.
  • separators In the field of lithium-sulfur cells separators are desired, which also prevent the early cell death of lithium-sulfur cells, which is favored in particular by the migration of polysulfide ions from the cathode to the anode. It is an object of the present invention to provide a low-cost separator for a long-lived electrochemical cell, in particular a lithium-sulfur cell, which has advantages over one or more properties of a known separator, in particular a separator having a good lithium-ion permeability, high temperature stability and good mechanical properties shows.
  • composite materials according to the invention are composite materials which in the context of the present invention are also called composite materials according to the invention.
  • Composite materials are generally understood to mean materials which are solid mixtures which can not be separated manually and which have different properties than the individual components.
  • composite materials according to the invention are fiber composites.
  • the main body of nonwoven fabric (A) partially to completely from the Nanocomposite matenal (B) be penetrated.
  • the main body of nonwoven fabric can be penetrated symmetrically or asymmetrically, that is, opposite sides of the body of nonwoven fabric can differ from each other.
  • the composite material according to the invention is characterized in that the base body of nonwoven fabric (A) is at least partially, preferably more than 50%, in particular completely penetrated by the nanocomposite material (B).
  • the composite material according to the invention comprises as component (A) at least one main body made of nonwoven fabric, also referred to as nonwoven fabric (A) in the context of the present invention.
  • nonwoven fabric also referred to as nonwoven fabric (A) in the context of the present invention.
  • Nonwovens and their preparation are known in the art. Commercially, a wide range of nonwovens is available.
  • a nonwoven fabric of inorganic or organic materials preferably made of organic materials.
  • inorganic nonwovens examples include glass fiber nonwovens and ceramic fiber nonwovens.
  • organic polymers for producing nonwovens are polyolefins, in particular polyethylene or polypropylene, polymers of heteroatom-containing vinyl monomers, in particular polyacrylonitrile, polyvinylpyrrolidone or polyvinylidene fluoride, polyesters, in particular polybutyl terephthalate, polyethylene terephthalate or polyethylene naphthalate, polyamides, in particular PA 6, PA 11 , PA 12, PA 6.6, PA 6.10 or PA 6.12, polyimides, polyetheretherketones, polysulfones or polyoxymethylene.
  • polyolefins in particular polyethylene or polypropylene
  • polymers of heteroatom-containing vinyl monomers in particular polyacrylonitrile, polyvinylpyrrolidone or polyvinylidene fluoride
  • polyesters in particular polybutyl terephthalate, polyethylene terephthalate or polyethylene naphthalate
  • polyamides in particular PA 6, PA 11 , PA 12, PA 6.6, PA 6.10
  • the composite material according to the invention is characterized in that the main body of nonwoven fabric (A) is made of organic polymers which are selected from the group of polymers consisting of polyolefins, in particular polyethylene and polypropylene, polymers of heteroatom-containing Vinyl monomers, in particular polyacrylonitrile, polyvinylpyrrolidone and polyvinylidene fluoride, polyesters, in particular polybutyl terephthalate, polyethylene terephthalate and polyethylene naphthalate, polyamides, in particular PA 6, PA 11, PA 12, PA 6.6, PA 6.10 and PA 6.12, polyimides, polyether ether ketones, polysulfones and polyoxymethylene are. Particular preference is given to nonwovens (A) which are made of polyester, in particular of polyethylene terephthalate.
  • the base body made of nonwoven fabric is preferably a sheet-like basic body, wherein in the context of the present invention the term "sheet-like" means that the basic body described, a three-dimensional body, in one of its three spatial dimensions (expansions), namely Thickness is smaller than in the other two dimensions, the length and the width.
  • the thickness of the main body is at least a factor of 5, preferably at least a factor of 10, more preferably at least 20 times smaller than the second largest extent.
  • the composite material containing the main body (A) also preferably constitutes a sheet-like body.
  • the composite material according to the invention is characterized in that the composite material is a sheet-like body.
  • the base body of nonwoven preferably has a thickness in the range of 5 to 100 ⁇ , particularly preferably 10 to 50 ⁇ , in particular 15 to 25 ⁇ on.
  • the fibers from which the nonwoven fabric is made usually have a fiber length which exceeds the mean diameter of the fibers by at least two times, preferably a multiple.
  • the average diameter of at least 90% of the fibers contained in the non-woven is preferably at most 20 ⁇ , more preferably at most 12 ⁇ , in particular between 4 and 6 ⁇ .
  • the porosity of the base body of nonwoven fabric is preferably in the range of 50 to 80%, preferably in the range of 50 to 60%.
  • the composite material according to the invention comprises as component (B) at least one nanocomposite material, in the context of the present invention also called nanocomposite (B) for short, which
  • Nanocomposites (B), as defined above, are known in principle and are accessible in different macroscopic forms, the microscopic structure of phases (a) and phases (b) being substantially identical, that is, phase (a) and phase (b) being substantially identical. form substantially co-continuous phase domains, wherein the average distance between two adjacent domains of identical phases is at most 100 nm.
  • WO2010 / 1 12581 pages 30 to 31 describes various nanocomposites (B) as solids.
  • page 38 line 1 to page 41, line 26, particulate nanocomposites (B) are described, and in WO 201 1/000858, page 6, line 24 to page 12, line 28, nanocomposites (B) are described as porous Foil materials described.
  • WO 2010/128144 page 38, line 1 to page 41, line 26, particulate nanocomposites (B) are described, and in WO 201 1/000858, page 6, line 24 to page 12, line 28, nanocomposites (B) are described as porous Foil materials described.
  • the preferred embodiments of the nanocomposite (B) and the explanations concerning the terms of the phases and phase domains reference is made in full to those parts of the text which are hereby made part of the description of the present invention.
  • the metal or semimetal M in the inorganic or (semi-) organometallic phase (a) is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof , M is especially selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% or the total amount of all metals or semimetals M is equal to silicon.
  • the composite material according to the invention is characterized in that the metal or metalloid M of phase (a) is selected among B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof, is preferably selected from B, Al, Si, Ti, Zr and Sn, is particularly preferably selected among Al, Si, Ti and Zr, in particular, is selected from Si.
  • the composite material according to the invention is characterized in that the metal or semimetal M comprises at least 90 mol%, in particular at least 99 mol%, based on the total amount of M, silicon.
  • the composite material according to the invention comprises as component (C) at least one polyether or at least one polyether-containing radical, the polyether-containing radical being covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b).
  • component (C) at least one polyether or at least one polyether-containing radical, the polyether-containing radical being covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b).
  • Polyethers and their preparation are known in principle to the person skilled in the art. Thus, a variety of polyethers is commercially available. Preferably, many of these polyethers contain the monomer units ethylene oxide or propylene oxide, in particular ethylene oxide. Both cyclic and linear polyethers are known. An example of a defined cyclic polyether is, for example, [18] crown-6.
  • linear polyethers are in particular polyalkylene glycols, preferably poly-C 1 -C 4 -alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
  • polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be in the range of at least 200 g / mol up to 100,000 g / mol, preferably from 400 g / mol up to 10,000 g / mol.
  • Polyethers preferred as component (C) are selected from the group of polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide.
  • polyether-containing radicals their production and handling are also known to the person skilled in the art. Since polyether-containing radicals are derived in principle from a polyether as described above, for example by abstraction of a hydrogen atom from a hydrocarbon fragment or preferably an OH group of the relevant polyether, the polyether-containing radicals are based in particular on the monomer units ethylene oxide or propylene oxide, in particular ethylene oxide ,
  • the polyether-containing radical which is covalently bound to the (semi-) organometallic phase (a) or organic polymer phase (b) is preferably directly via an oxygen atom of the polyether-containing radical or in particular via a divalent hydrocarbon fragment, for example a methylene group, Ethylene group, propylene group or a Phenylengrup- pe connected to one of the two phases.
  • a polyether-containing radical which contains monomer units selected from the group consisting of ethylene oxide and propylene oxide via a C atom with the (semi-) organometallic phase (a), in particular with the metal or semimetal M of the (semi-) organometallic phase (a), in particular with Si, connected.
  • the proportion by weight of the entire component (C), that is to say of the at least one polyether or of the at least one polyether-containing radical, based on the total weight of the composite material is preferably between 5 and 60% by weight, particularly preferably between 30 and 50% by weight.
  • the proportion by weight of the total nanocomposite material (B) based on the total weight of the composite material is preferably at least 20% by weight, more preferably at least 30% by weight and may be up to a maximum of 99% by weight, preferably up to 95% by weight. -%.
  • the composite material according to the invention may optionally comprise at least one lithium salt as component (D).
  • the composite material according to the invention preferably comprises at least one lithium salt as component (D).
  • component (D) is such a lithium salt which is commonly used as a conductive salt in lithium-ion cells.
  • the lithium salt (D) is particularly preferably selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate.
  • the composite material according to the invention is characterized in that the lithium salt (D) is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate.
  • the lithium salt (D) is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium (bis (trifluoromethylsulfonyl) imide) and lithium tetrafluoroborate.
  • the composite material according to the invention may comprise as further constituent a component (E) which is at least one inorganic (semi-) metal oxide in the form of particles.
  • a component (E) which is at least one inorganic (semi-) metal oxide in the form of particles.
  • inorganic (semi-) metal oxides are silicates, aluminates, titanium dioxides, barium titanate, zirconium dioxide or yttrium oxide.
  • the component (B) of the composite material according to the invention namely the nanocomposite (B), is preferably a polymerization product of at least one monomer AB, which
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerizable organic monomer unit B which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,
  • the polymerization product is obtained under cationic polymerization conditions under which both the polymerizable monomer unit A and the polymerizable monomer unit B polymerize to break the bond between A and B, and wherein the Monomer AB in the presence of the main body of nonwoven fabric (A), the polyether or the polyether-containing radical (C) and optionally the lithium salt (D) is polymerized.
  • the composite material according to the invention is characterized in that the nanocomposite material (B) is a polymerization product of at least one monomer AB which
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerisable organic monomer unit B which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,
  • the polymerization product is obtained under cationic polymerization conditions under which polymerize both the polymerizable monomer unit A and the polymerizable monomer unit B breaking the bond between A and B, and wherein the monomer AB in the presence of the base body of nonwoven fabric (A), the polyether or the polyether-containing radical (C) and optionally the lithium salt (D) is polymerized.
  • the preparation of the composite materials according to the invention is achieved by a process which comprises a so-called twin polymerization of the monomers AB explained in more detail below under cationic polymerization conditions, wherein the monomer AB in the presence of the main body of nonwoven fabric (A), the polyether or the polyether-containing radical ( C) and optionally the lithium salt (D) is polymerized.
  • the components (A), (C) and (D) have already been explained in detail above.
  • twin polymerization of so-called “twin monomers” is described, for example, in WO 2010/112581, page 2, line 16 to page 4, line 11 or in WO 201 1/000858, page 14, line 29 to page 16, line 7
  • a twin copolymerization of two different (twin) monomers is explained in detail, for example, in WO 201 1/000858, page 16, line 9 to page 24, line 11.
  • Another object of the present invention is therefore also a method for producing a composite material comprising the components
  • a nanocomposite material wherein the organic polymer phase (b) and the inorganic or (semi-) metal organic phase (a) form substantially co-continuous phase domains, wherein the mean distance between two adjacent domains of identical phases is at most 100 nm;
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerizable organic monomer unit B which is connected via one or more covalent chemical bonds to the polymerizable monomer unit A,
  • the metal or semimetal M of the monomer unit A in the monomers AB is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof.
  • M is in particular selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, in particular Si. Particularly preferred are at least 90 mol%, especially at least 99 mol% or the total amount of all metals or semimetals M is equal to silicon.
  • the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A in the monomers AB is selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof, preferably selected from B, Al, Si, Ti, Zr and Sn, more preferably selected from Al, Si, Ti and Zr, in particular is selected from Si.
  • the method according to the invention for producing a composite material is characterized in that the metal or semimetal M of the monomer unit A is at least 90 mol%, in particular at least 99 mol%, based on the total amount of M, silicon includes.
  • M is a metal or semimetal
  • R, R 2 may be the same or different and each represents a radical
  • radicals R 1 Q and R 2 G together represent a radical of the formula Ia
  • R may be identical or different and are halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl are selected and R a , R b have the meanings given above;
  • G is O, S or NH, in particular O;
  • Q is O, S or NH, in particular O;
  • q corresponding to the valence of M is 0, 1 or 2
  • X, Y may be the same or different and each is O, S, NH or a chemical
  • Bond in particular O or a chemical bond
  • R 1 ', R 2 ' may be the same or different and each is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar '-C (R a ', R b ') - are in which Ar' has the meanings given for Ar and R a ', R b ' have the meanings given for R a , R b or R 1 ', R 2 ' together with
  • X and Y are a radical of the formula Ia as defined above; or, when X is oxygen, the radical R 1 'is a radical of the formula Ib: in which q, R 1 , R 2 , R 2 ' , Y, Q and G have the meanings given above and # denotes the bond to X.
  • the moieties corresponding to the radicals R 1 and R 2 G form polymerisable unit (s) B. If X and Y are different from a chemical bond and R 1 ' X and R 2' do not represent inert radicals such as C i C6-alkyl, C3-C6-cycloalkyl or aryl, the radicals R 1 ' X and R 2' Y also form polymerizable unit (s) B. On the other hand forms the metal atom M, optionally together with the groups Q and Y, the Main component of the monomer unit A.
  • an aromatic radical or aryl
  • a carbocyclic aromatic hydrocarbon radical such as phenyl or naphthyl.
  • a heteroaromatic radical or hetaryl is understood as meaning a heterocyclic aromatic radical which generally has 5 or 6 ring members, one of the ring members being a heteroatom which is selected from nitrogen, oxygen and sulfur and, if appropriate 1 or 2 further ring members may be a nitrogen atom and the remaining ring members are carbon.
  • heteroaromatic radicals are furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrdazinyl or thiazolyl.
  • a condensed aromatic radical or ring is understood as meaning a carbocyclic aromatic, divalent hydrocarbon radical, such as o-phenylene (benzo) or 1,2-naphthylene (naphtho).
  • a fused heteroaromatic radical or ring is understood as meaning a heterocyclic aromatic radical as defined above, in which two adjacent C atoms form the double bond shown in formula Ia or in the formulas I I and I I I.
  • the metal or metalloid M in formula I is in particular for the preferred embodiments of M. given in connection with the description of the composite material.
  • the groups R 1 Q and R 2 G together represent a radical of the formula Ia as defined above, in particular a radical of the formula Iaa:
  • twin monomers of the first embodiment preference is furthermore given to those monomers of the formula I in which q is 0 or 1 and in which the group XR 1 'is a radical of the formula Ia' or Iaa ':
  • M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,
  • Sb or Bi particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;
  • A, A 'independently represent an aromatic or heteroaromatic ring fused to the double bond
  • n are independently 0, 1 or 2, in particular 0;
  • G, G 'independently represent O, S or NH, in particular O or NH and especially O;
  • Q, Q 'independently represent O, S or NH, in particular O;
  • R, R ' are independently halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and
  • R a , R b , R a ' , R b' are independently selected from hydrogen and methyl or
  • L represents a group (YR 2 ' ) q in which Y, R 2' and q have the meanings given above and
  • M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,
  • Sb or Bi particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;
  • n are independently 0, 1 or 2, in particular 0;
  • R a , R b , R a ' , R b' are independently selected from hydrogen and methyl or
  • R a and R b and / or R a and R b ' are each together an oxygen atom; in particular, R a , R b , R a ' , R b' are each hydrogen;
  • L is a group (YR 2 ' ) q , wherein Y, R 2' and q have the meanings given above.
  • Such monomers are known from WO2009 / 083082 and WO2009 / 083083 or can be prepared by the methods described therein.
  • Another example of a monomer IIa is 2,2-spirobi [4H-1,2,2-benzodioxaborine] (Bull. Chem. Soc. Jap.
  • the moiety MQQ 'or MO2 forms the polymerizable unit A, whereas the remaining portions of the monomers II and IIa, i. the groups of the formulas Ia and Iaa minus the atoms Q and Q '(or minus the oxygen atom in laa) form the polymerizable units B.
  • M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,
  • Sb or Bi particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;
  • A is an aromatic or heteroaromatic ring fused to the double bond
  • n 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Q is O, S or NH, in particular O;
  • R is independently selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl and is in particular methyl or methoxy;
  • R a , R b are independently selected from hydrogen and methyl or R a and
  • R c , R d are identical or different and are each selected from C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl and are in particular methyl ,
  • M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,
  • Sb or Bi particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;
  • n 0, 1 or 2, in particular 0;
  • G is O, S or NH, in particular O or NH and especially O;
  • Radicals R are independently halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and
  • Phenyl selected and are in particular methyl or methoxy
  • R a , R b are independently selected from hydrogen and methyl or R a and
  • R c , R d are identical or different and in each case selected from Ci-C6-alkyl, C3-C6-cycloalkyl, polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl and are in particular for methyl.
  • Such monomers are known, for example, from Wieber et al. Journal of Organometallic Chemistry, 1, 1963, 93, 94. Further examples of monomers Ia are 2,2-diphenyl [4H-1,2,2-benzodioxasiline] (J. Organomet. Chem. 71 (1974) 225);
  • the monomers of the formula III or IIIa are preferably not copolymerized alone but in combination with the monomers of the formulas II or IIa.
  • the monomers AB of the general formula I are those which are described by the general formula IV,
  • M is a metal or semimetal, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V,
  • Sb or Bi particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si;
  • Ar, Ar ' are the same or different and are each an aromatic or heteroaromatic ring which optionally has 1 or 2 substituents which are listed under
  • Halogen, CN, Ci-C6-alkyl, Ci-C6-alkoxy and phenyl are selected;
  • R a , R b , R a ' , R b' are independently selected from hydrogen and methyl or
  • R a and R b and / or R a ' and R b' each together represent an oxygen atom; q corresponding to the valence of M is 0, 1 or 2;
  • X, Y may be the same or different and represent O, S, NH or a chemical bond
  • R 1 ' , R 2' may be the same or different and each is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar "-C (R a” , R b " ) - in which Ar” has the meanings given for Ar and R a " ,
  • R b "have the meanings given for R a , R b or R 1 ' , R 2' together with X and Y represent a radical of the formula A as defined above.
  • the monomer AB is not copolymerized alone but in combination with at least one monomer A1 B1, wherein the monomer AB is at least a first cationically polymerizable monomer unit A, which is a metal or semimetal M and at least one of M covalently via a C atom-bonded radical selected from the group Ci-C2o hydrocarbon radical and polyether-containing radical having.
  • the method according to the invention for producing a composite material is characterized in that it is in the polymerization of at least one monomer AB to a copolymerization of at least one monomer AB, the
  • At least one first cationically polymerizable monomer unit A which is a metal or metalloid M and at least one M bonded to M, bonded via a carbon atom selected from the group Ci-C2o-hydrocarbon radical, preferably Ci-C4-alkyl, especially methyl, and polyether -containing radical, in particular a polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, preferably ethylene oxide, and
  • At least one second cationically polymerisable organic monomer unit B which is connected via one or more covalent chemical bonds to the polymerisable unit A,
  • At least one second cationically polymerizable organic monomer unit B1 which is connected to the polymerizable monomer unit A1 via one or more covalent chemical bonds,
  • the copolymerization of the monomers AB with the monomers A1 B1 is characterized in that M in the monomers AB and in the monomers A1 B1 independently of one another represents Si, Al, Ti or Zr, in particular Si, and the cationically polymerizable organic Monomer units B and B1 in the corresponding monomers AB and A1 B1 are each covalently bonded to M via one or more oxygen atoms.
  • the copolymerization of the monomers AB with the monomers A1 B1 is characterized in that in the monomer AB the metal or semimetal M is Si and the monomer unit A is two identical or different, in each case via a carbon atom Si has bonded radicals which are selected from the group consisting of C 1 -C 18 -alkyl, vinyl, C 6 -C 10 -aryl, C 7 -C 14 -alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, in particular special ethylene oxide.
  • the monomer A1 B1 is in principle defined as the monomer AB and can generally also be described by the general formula I. More preferably, the monomer A1 B1 is characterized by the general formulas II or IIa described above.
  • monomers AB or A1 B1 of the general formula I preference is given to 2,2'-spiro [4H-1,2,2-benzodioxasiline], 2,2-dimethyl- [4H-1,2,2-benzodioxasiline], 2 2-diphenyl- [41-1-1,2,2-benzodioxasiline], 2,2-dialkyl- [4H-1,2,2-benzodioxasiline], 2-alkyl-2-methyl- [4H-1,3 , 2-benzodioxasilin], 2-methyl-2-vinyl- [4H-1, 3,2-benzodioxasilin] or the compounds mentioned in WO 201/000858 on page 20, lines 7 to 18 in the polymerization step for the preparation of
  • the molar ratio of the two monomers can be varied within a wide range.
  • the molar ratio of the monomers AB and A1 B1 to one another is in the range from 5:95 to 9: 1, frequently in the range from 1: 9 to 4: 1 or 1: 4 to 2: 1, in particular in the range from 1: 2 to 6: 4.
  • AB is a monomer containing a polyether-containing radical of AB are used at most 50 wt .-% based on the total weight of the monomers used and at the same time at least 50 wt .-% of a Monomers A1 B1 of the general formula II or IIa used.
  • the polymerization of at least one monomer AB or the copolymerization of at least one monomer AB with at least one monomer A1 B1 can advantageously be carried out in the presence of a polyether, whereby the component (C) contained in the composite material is then added to the polyether used in the process equivalent.
  • the monomer AB does not have to contain a polyether-containing radical.
  • the polyethers which can be used as component (C) and their preferred embodiments have already been explained in connection with the description of component (C) of the composite material according to the invention.
  • component (C) is a polyether selected from the group comprising polyethylene glycols, polypropylene glycols and copolymers of ethylene oxide and propylene oxide.
  • the inventive method for producing a composite material is characterized in that the polymerization in the presence of another component (E), which is at least one inorganic (semi-) metal oxide in the form of particles is performed.
  • another component (E) which is at least one inorganic (semi-) metal oxide in the form of particles. Examples of such particles have already been mentioned above in connection with the description of component (E) of the composite material according to the invention.
  • the polymerization conditions are selected in the process according to the invention such that in the copolymerization of the monomers AB and A1 B1 the monomer units which carry the inorganic form nic or (semi-) organometallic phase (a), and polymerize monomer units which form the organic polymer phase (b), ie the cationically polymerizable organic moiety synchronously.
  • the term "synchronous” does not necessarily mean that the polymerization of the first and second monomer units proceeds at the same rate. Rather, “synchronous” means that the polymerization of the first and second monomer units are kinetically coupled and triggered by the same polymerization conditions.
  • a synchronous polymerization is ensured if the copolymerization is carried out under cationic polymerization conditions.
  • the copolymerization of the monomers AB and A1 B1, in particular the copolymerization of the monomers of the previously defined general formulas III or IIIa with monomers of the general formulas II or IIa, is carried out in particular under protic catalysis or in the presence of aprotic Lewis acids.
  • Preferred catalysts here are Bronsted acids, for example organic carboxylic acids such as.
  • Trifluoroacetic acid Trifluoroacetic acid, trichloroacetic acid, formic acid, chloroacetic acid, dichloroacetic acid, hydroxyacetic acid (glycolic acid), lactic acid, cyanoacetic acid, 2-chloropropanoic acid, 2,3-bishydroxypropanoic acid, malic acid, tartaric acid, mandelic acid, benzoic acid or o-hydroxybenzoic acid, as well as organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or toluenesulfonic acid. Also suitable are inorganic Bronsted acids such as HCl, H2SO4 or HCIO4.
  • Lewis acid for example, BF3, BC, SnCU, TiCU, or AICI3 can be used.
  • the use of complexed or dissolved in ionic liquids Lewis acids is also possible.
  • the acid is usually used in an amount of 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the total weight of the monomers.
  • Preferred catalysts are organic carboxylic acids, in particular organic carboxylic acids having a pKa value (25 ° C) in the range of 0 to 5, especially 1 to 4, z.
  • the polymerization can be carried out in bulk or preferably at least partially in an inert solvent or diluent.
  • Suitable solvents or diluents are organic solvents, for example halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethene, chlorobutane or chlorobenzene, aromatic hydrocarbons such as toluene, xylenes, cumene or tert-butylbenzene, aliphatic and cycloaliphatic hydrocarbons such as cyclohexane or hexane, cyclic or alicyclic Ethers such as tetrahydrofuran, dioxane, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, diisopropyl ether and mixtures of the abovementioned organic solvents.
  • organic solvents in which the monomers AB and A1B1 are sufficiently soluble under polymerization conditions include in particular aromatic hydrocarbons, cyclic and alicyclic ethers and mixtures of these solvents.
  • the polymerization of the monomer AB or the copolymerization of the monomers AB and A1 B1 is carried out in the substantial absence of water, i. H. the concentration of water at the beginning of the polymerization is less than 0.1% by weight.
  • monomers AB and A1 B1 or as monomers of the formula I those monomers are preferred which do not split off any water under polymerization conditions. These include in particular the monomers of the formulas II, IIa, III and IIIa.
  • the polymerization can in principle be carried out in a wide temperature range, preferably in the range from 0 to 200 ° C., in particular in the range from 20 to 120 ° C.
  • the inventive method for producing a composite material is characterized in that the polymerization is carried out at a temperature between 0 and 200 ° C.
  • the process according to the invention for producing a composite material is preferably carried out in such a way that the composite material which forms during the polymerization is produced directly in the form of a thin layer.
  • a base body of nonwoven fabric with the starting compounds of the other components, that is in particular the monomer AB or the monomers AB and A1 B1 and optionally the polyether as component (C), the conductive salt (D) and / or the loaded inorganic (half) metal oxide particles (E) and in a second process step, the monomer AB or the monomers AB and A1 B1 to the nanocomposite material (B) is reacted in which the components (C), (D) and (E ) are chemically embedded unchanged.
  • a nonwoven fabric can be loaded or filled partially or completely with the necessary starting components by impregnation, brushing, doctor blade methods, calendering methods or combinations thereof.
  • a nonwoven fabric filled in this way is then subjected to conditions under which the polymerization or copolymerization takes place.
  • the resulting composite materials are particularly suitable as a separator or as part of a separator in electrochemical cells.
  • batteries, capacitors and batteries secondary batteries of any kind, especially alkali metal cells or batteries such.
  • lithium, lithium ion, lithium-sulfur and alkaline earth batteries and accumulators and in the form of high-energy or high-performance systems, as well as electrolytic capacitors and double-layer capacitors, which are called Supercaps, Goldcaps, BoostCaps or Ultracaps are known.
  • Another object of the present invention is a use of the above-described composite material according to the invention as a separator or as part of a separator in electrochemical cells, fuel cells or supercapacitors.
  • a separator for an electrochemical cell in particular consisting of the above-described composite material according to the invention.
  • the present invention is a fuel cell, a battery or a capacitor, comprising at least one separator according to the invention, as described above.
  • the composite materials according to the invention are suitable for electrochemical cells which are based on the transfer of alkali metal ions, in particular for lithium metal, lithium sulfur and lithium ion cells or batteries and especially for lithium ion secondary cells or Secondary batteries.
  • Particularly suitable are the composite materials according to the invention for electrochemical cells from the group of lithium-sulfur cells.
  • the subject of the present invention is an electrochemical cell containing
  • 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.
  • Particularly preferred electrochemical cells are therefore lithium-ion cells, in particular lithium-ion secondary cells, which have at least one separator layer, which is composed of the composite materials according to the invention.
  • Such cells generally have at least one anode suitable for lithium-ion cells, a cathode suitable for lithium-ion cells, an electrolyte and at least one separator layer arranged between the anode and the cathode and comprising composite materials according to the invention.
  • suitable cathode materials suitable anode materials, suitable electrolytes and possible arrangements, reference is made to the relevant prior art, eg. B. on appropriate monographs and reference works: z. Wakihara et al.
  • cathodes in which the cathode material comprises a lithium transition metal oxide, eg. 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, a lithium sulfide or lithium polysulfide such as L12S, L12S8, L12S6, L12S4, or L12S3, or a lithium transition metal phosphate such as lithium iron phosphate as the electroactive component. Also suitable are cathode materials containing iodine, oxygen, sulfur and the like as the electroactive component.
  • a lithium transition metal oxide eg.
  • 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
  • a lithium sulfide or lithium polysulfide such as
  • the electrochemical cell according to the invention also contains at least one anode (Y).
  • anode (Y) may be selected from anodes of carbon, anodes containing Sn or Si, and anodes containing lithium titanate of formula Li 4 + x Ti 5 O 2 with x equal to a numerical value of> 0 to 3
  • 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 (Y) 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.
  • anodes and cathodes may also contain other ingredients, for example
  • electrically conductive or electroactive components such as carbon black, graphite, carbon fibers, nanocarbon fibers, nanocarbon tubes or electrically conductive polymers;
  • Binder such as polyethylene oxide (PEO), cellulose, carboxymethylcellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene rafluoroethylene, styrene-butadiene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polyvinylidene difluoride (PVdF), polyvinylidene difluoride-hexafluoropropylene copolymers (PVdF-HFP), tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymers, vinylidene fluoride-hexafluoropropylene Copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotri
  • Copolymers ethylene-chlorofluoroethylene copolymers, ethylene-acrylic acid copolymers (with and without inclusion of sodium ions), ethylene-methacrylic acid copolymers (with and without inclusion of sodium ions), ethylene-methacrylic acid ester copolymers (with and without inclusion of sodium ions), Polyimides and polyisobutene.
  • the two electrodes, d. H. the anode and the cathode are connected together using a separator according to the invention and a liquid or else solid electrolyte in a manner known per se.
  • a separator according to the invention for example, a composite material according to the invention on one of the two electrodes, which is provided with a current conductor, (anode or cathode) apply, for. B. laminate, soak with the electrolyte, and then apply the oppositely charged electrode, which is provided with a current collector, wrap the resulting sandwich if necessary, and bring in a battery case.
  • non-aqueous solutions water content of generally ⁇ 20 ppm
  • lithium salts and molten Li salts are suitable as liquid electrolytes, eg.
  • a separator layer according to the invention is arranged, which is soaked in the rule with the liquid, in particular a liquid organic electrolyte.
  • 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. Examples of mobile devices are vehicles, for example automobiles, two-wheeled vehicles, aircraft or watercraft, such as boats or ships. Other examples of mobile devices are those that you move yourself, 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 according to the invention which contain 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 monomers AB which can be used in the process according to the invention for producing the composite material according to the invention, which contain at least one polyether-containing radical, are new.
  • Such special monomers AB can be prepared by known methods which can also be used for the preparation of the monomers AB known from the literature, the introduction of the polyether-containing radical being carried out by methods which are known to a person skilled in the art, in particular to an organic chemist.
  • Another object of the present invention is also a monomer AB, the
  • At least one first cationically polymerizable monomer unit A which has a metal or semimetal M
  • At least one second cationically polymerizable organic monomer unit B which is connected via one or more covalent chemical bonds to the metal or metalloid M of the polymerizable monomer unit A,
  • the monomer AB contains at least one polyether-containing radical.
  • a monomer AB according to the invention in which M is Si, the cationically polymerizable organic monomer unit B is covalently bonded to M via two oxygen atoms and the monomer unit A has two identical or different radicals which are bonded to Si via a carbon atom are from the group consisting of Ci-cis-alkyl, vinyl, C6-C10 aryl, C7-C14 alkylaryl and polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, wherein at least one of the two via a C-atom bonded to Si is a polyether-containing radical.
  • monomer AB is selected from compounds of general formula IIIa '
  • R may be the same or different and are selected from halogen, CN, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and phenyl,
  • n 0, 1 or 2, in particular 0,
  • R a , R b independently of one another represent hydrogen or methyl, in particular hydrogen
  • Rr is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, a polyether-containing radical bonded via a carbon atom, containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, and aryl or a radical Ar'-C (R a ').
  • R b ' ) - are, in which Ar' has the meanings given for Ar and R a ' , R b' have the meanings given for R a , R b , and
  • R 2 ' is a bonded via a carbon atom polyether-containing radical containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, in particular ethylene oxide.
  • 'R is preferably C 1 -C 6 -alkyl, in particular methyl.
  • preferred monomer AB is characterized in that the polyether-containing radical bonded to Si via a C atom is a radical of the formula C-PEG, wherein
  • o is 0 or an integer from 1 to 18, preferably 1 to 6, in particular 1
  • n is an integer from 1 to 100, preferably 5 to 50, in particular 8 to 30.
  • the invention is illustrated by the following, but not limiting examples of the invention.
  • R3S1CH2CH2CH2OR 1, 4-1, 5 ppm (2 H, m, R3S1CH2CH2CH2OR), 3.15 ppm (3H, s, -OCH3), 3.2 - 3.3 ppm (2H, dd, R3S1CH2CH2CH2OR), 3, 3 - 3.5 (44H, m, R (OCH 2 CH 2 ) 2 OCH 3), 4.75 ppm (2
  • R3S1CH2CH2CH2OR 1, 3 -1, 4 ppm (2 H, m, R3S1CH2CH2CH2OR), 3.05 ppm (3H, s, -OCH3), 3.1-3.2 ppm (2H, dd, R3S1CH2CH2CH2OR) 3.3 to 3.5 (88H, m, R (OCH2CH2) 22 OCH 3), 4.6 ppm (2 H, s, Ar-CH 2 -O), 6.5 to 6.9 ppm (4H, m, Ar-H).
  • Polyethylene glycol methyl ether having a molecular weight of about 500 g / mol (commercially available as Pluriol A 500E ® from BASF SE) and Lithiumtrifluorsulfonklaimid (LiTFSI) were homo genie carbonized at 85 ° C. To this was added 266 mg (1.6 mmol) of 2,2-dimethyl- [4H-1,2,3-benzodioxasiline] (prepared according to Tetrahedron Lett. 24 (1983) 1273).
  • the reactive monomer mixture was polymerized for 10 minutes at 95 ° C. and fractionated onto a metal plate with PET nonwoven (commercially available as fleece "PES20" from APODIS Filtertechnik OHG, 8 g / m.sup.2, thickness ) , prewarmed to 95 ° C. in the desiccator 20 ⁇ , 5 x 3.5 cm surface), so that sheet-like composite materials were obtained with layer thicknesses of 30 to 90 ⁇ then polymerized in a drying oven at 95 ° C for 3 h under a stream of nitrogen and then annealed at 195 ° C for After 30 minutes under vacuum.
  • PET nonwoven commercially available as fleece "PES20" from APODIS Filtertechnik OHG, 8 g / m.sup.2, thickness
  • Electrolyte 1 M LiTFSI in dioxolane and dimethyl ether (1: 1 vol / vol)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Cell Separators (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polyethers (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un nouveau matériau composite comprenant au moins un corps de base constitué de non-tissé en tant que composant (A), au moins un matériau nanocomposite en tant que composant (B), au moins un polyéther ou au moins un groupe contenant du polyéther en tant que composant (C) et éventuellement un sel de lithium en tant que composant (D). Cette invention concerne en outre un procédé pour produire ce nouveau matériau composite, son utilisation dans des séparateurs pour cellules électrochimiques ainsi que des composés de départ spécifiques qui peuvent être employés pour produire un matériau nanocomposite (B).
EP12866500.7A 2012-01-23 2012-12-14 Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques Withdrawn EP2807209A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12866500.7A EP2807209A4 (fr) 2012-01-23 2012-12-14 Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12152129 2012-01-23
EP12866500.7A EP2807209A4 (fr) 2012-01-23 2012-12-14 Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques
PCT/IB2012/057308 WO2013110985A1 (fr) 2012-01-23 2012-12-14 Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques

Publications (2)

Publication Number Publication Date
EP2807209A1 true EP2807209A1 (fr) 2014-12-03
EP2807209A4 EP2807209A4 (fr) 2015-09-02

Family

ID=48872933

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12866500.7A Withdrawn EP2807209A4 (fr) 2012-01-23 2012-12-14 Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques

Country Status (5)

Country Link
EP (1) EP2807209A4 (fr)
JP (1) JP2015512957A (fr)
KR (1) KR20140116948A (fr)
CN (1) CN104066776A (fr)
WO (1) WO2013110985A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8865858B2 (en) 2012-06-26 2014-10-21 Basf Se Process for producing a composite material
WO2014001949A1 (fr) * 2012-06-26 2014-01-03 Basf Se Matériaux composites et leur procédé de fabrication
WO2015086461A1 (fr) * 2013-12-13 2015-06-18 Basf Se Matériaux composites contenant de l'azote, leur fabrication et utilisation
DE102014206040A1 (de) 2014-03-31 2015-10-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Elektrochemische Zelle mit einem organisch-anorganischen Hybridmaterial und Verwendungen eines anorganisch-organischen Hybridmaterials
CN105047886A (zh) * 2015-06-18 2015-11-11 田东 一种锂离子电池石墨负极浆料及其制备方法
CN104993119A (zh) * 2015-06-18 2015-10-21 田东 一种锂离子电池钛酸锂负极浆料及其制备方法
CN107039623A (zh) * 2017-03-24 2017-08-11 江苏乐能电池股份有限公司 一种改善锂离子电池低温性能的复合隔膜及其锂离子电池
CN112635840B (zh) * 2020-12-21 2021-12-14 中南大学 一种HNTs增塑PAN/P(LLA-EG-MA)生物凝胶聚合物电解质的制备方法及其产品
CN114122400B (zh) * 2021-11-03 2024-05-28 珠海冠宇电池股份有限公司 一种负极极片及含该负极极片的锂离子电池
CN115312892B (zh) * 2022-10-10 2023-03-24 宁德新能源科技有限公司 电化学装置及电子设备

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10208277A1 (de) * 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Elektrischer Separator, Verfahren zu dessen Herstellung und Verwendung
US20030180624A1 (en) * 2002-03-22 2003-09-25 Bookeun Oh Solid polymer electrolyte and method of preparation
CN102388106B (zh) * 2009-04-03 2014-04-23 巴斯夫欧洲公司 制备复合材料的方法
CN102459285A (zh) * 2009-05-08 2012-05-16 巴斯夫欧洲公司 制备颗粒状纳米复合材料的方法
US8603681B2 (en) * 2009-07-01 2013-12-10 Basf Se Porous film material comprising at least one carbonaceous semimetal oxide phase, and use thereof as a separator material for electrochemical cells
US20120187045A1 (en) * 2009-10-01 2012-07-26 Basf Se Method for separating substance mixtures by means of multiphase polymer films
JP5841311B2 (ja) * 2009-12-21 2016-01-13 東レ・ダウコーニング株式会社 油性原料の増粘剤またはゲル化剤、それを含有してなるゲル状組成物および化粧料もしくは外用剤の製造方法
CN102008901B (zh) * 2010-09-28 2012-11-21 朱惠芬 一种多用途水处理纳米材料复合膜的制备方法

Also Published As

Publication number Publication date
EP2807209A4 (fr) 2015-09-02
JP2015512957A (ja) 2015-04-30
CN104066776A (zh) 2014-09-24
WO2013110985A1 (fr) 2013-08-01
KR20140116948A (ko) 2014-10-06

Similar Documents

Publication Publication Date Title
EP2807209A1 (fr) Matiériau composite, sa production et son utilisation dans des séparateurs pour cellules électrochimiques
EP2449614A1 (fr) Matériau en feuille poreux comprenant au moins une phase d'oxyde semi-métallique carbonée et son utilisation comme matériau de séparation pour cellules électrochimiques
DE69838186T2 (de) Elektrolyt aus fester polymerzusammensetzung in homogenem zustand und herstellungsverfahren und kompositelektrode, lithiumpolymerbatterie und lithiumionenbatterie die diese verwenden und herstellungsverfahren
EP2415106B1 (fr) Materiau electroactif et son utilisation au sein d'anodes pour cellules aux ions lithium
WO2003075371A2 (fr) Cellule electrochimique pour une pile ion lithium a stabilite aux hautes temperatures amelioree
WO2013135353A1 (fr) Séparateur contenant du graphène pour batteries lithium-ion
DE102019100860A1 (de) Separatoren für lithiumhaltige elektrochemische Zellen und Verfahren zur Herstellung derselben
CN112740460B (zh) 锂金属负极以及包含其的锂金属电池
EP1087452A2 (fr) Particules d'oxyde mixtes de lithium revêtues et leur utilisation
EP2697844A1 (fr) Batterie lithium-ion à tension élevée
WO2013017217A1 (fr) Batterie lithium-ion
WO2011144317A1 (fr) Additif pour électrolytes dans des piles à ions lithium rechargeables
EP2742552A1 (fr) Cellules électrochimiques
WO2013135351A1 (fr) Graphène dans des batteries lithium-ion
EP2705558A1 (fr) Électrode pour batteries lithium-ion
US20130189550A1 (en) Composite, its production and its use in separators for electrochemical cells
DE102017109655A1 (de) Elektrodenmaterial und Komposit-Elektroden auf Basis eines Polymers und Kohlenstoff
EP2820693A1 (fr) Séparateurs pour cellules électrochimiques contenant des particules polymères
WO2013084116A1 (fr) Cellules électrochimiques contenant un polymère renfermant de l'azote
CN110945692A (zh) 非水系二次电池用电极活性物质及其制造方法
WO2013144842A1 (fr) Cellule électrochimique contenant un polymère à base de soufre
DE112014002574T5 (de) Produktionsverfahren für einen porösen Aluminiumkörper, poröser Aluminiumkörper, Stromkollektor, Elektrode und elektrochemische Vorrichtung
JPWO2019116959A1 (ja) イオン捕捉剤、リチウムイオン電池用セパレータ及びリチウムイオン二次電池
EP2865033A1 (fr) Matériaux composites et leur procédé de fabrication
DE102018200110A1 (de) Elektrochemische Zelle mit Komponenten aus einem organisch-anorganischen Hybridmaterial und weitere Verwendungen dieses Hybridmaterials

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: 20140825

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)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150804

RIC1 Information provided on ipc code assigned before grant

Ipc: B32B 27/28 20060101ALI20150729BHEP

Ipc: C08J 5/18 20060101AFI20150729BHEP

Ipc: B32B 27/18 20060101ALI20150729BHEP

Ipc: H01M 10/0525 20100101ALI20150729BHEP

Ipc: H01M 2/16 20060101ALI20150729BHEP

Ipc: B32B 5/02 20060101ALI20150729BHEP

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: 20160301