EP2668328A1 - Thin macroporous polymer films - Google Patents

Thin macroporous polymer films

Info

Publication number
EP2668328A1
EP2668328A1 EP11805844.5A EP11805844A EP2668328A1 EP 2668328 A1 EP2668328 A1 EP 2668328A1 EP 11805844 A EP11805844 A EP 11805844A EP 2668328 A1 EP2668328 A1 EP 2668328A1
Authority
EP
European Patent Office
Prior art keywords
welded
fibers
polymer
film according
equal
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Withdrawn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
EP11805844.5A
Other languages
German (de)
French (fr)
Inventor
Ekkehard Beer
Michael Kube
Matthias Pascaly
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2668328A1 publication Critical patent/EP2668328A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D25/00—Woven fabrics not otherwise provided for
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/555—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving by ultrasonic heating
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/04—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments in rectilinear paths, e.g. crossing at right angles
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture

Definitions

  • the invention relates to a film comprising polymer fibers, at least to the
  • a fiber is understood to be a thin structure in relation to the length, which is flexible and can absorb no tensile forces but only tensile forces. Fibers buckle under pressure. In nature and technology fibers usually occur in a larger composite, they form a specific structure. Fibers of very large, virtually unlimited length are filaments, fibers of limited length are staple fibers.
  • Staple fibers in turn divide into actually spinnable staple fibers and below a limit length of about 15 mm flock fibers.
  • a yarn according to DIN 60900 is a collective term for all linear textile structures. Thereafter, a yarn is analogous to a long, thin structure of one or more fibers. It is a textile intermediate that can be made into fabrics, crocheted, knitted and embroidered or used for sewing.
  • Porous films are usually obtained by subjecting films, e.g. Polymer films, perforated or damage their original structure mechanically or chemically. Such materials can be supplied to a wide variety of uses, for example as
  • Packaging materials, separation and filtration membranes or as separators are packaged, separation and filtration membranes or as separators.
  • German patent application DE 10 2009 047 440 discloses production and properties of thin, perforated films which are stable for coating or impregnation processes.
  • the films contain or are made of metal or polymer and are perforated by means of a laser emitting at a suitable wavelength.
  • open area An important variable that characterizes openwork material is the open area. It is given through the pores and is determined by considering the material as a two-dimensional structure and the area occupied by the pores in relation to the total set of the material occupied area. If the pores are arranged regularly, elementary cells can be found that can be used to determine the open area. The edge length of the patches can be selected, for example, equal to 100 times the pore diameter.
  • F max tensile strength
  • a porous film is obtained by densifying a woven or knitted fabric comprising or consisting of polymer fibers such that the fibers are welded together at least at their points of intersection and / or at least partly fused together or non-positively or positively connected to each other. After such treatment, the fibers have lost their original shape in cross-section, but are still recognizable as such, for example under light microscopic observation. By contrast, the macroscopic structure no longer has the properties of a conventional fabric or knitted fabric - individual threads or fibers can no longer be separated off.
  • the invention thus relates to a porous film, which is characterized in that the film comprises polymer fibers which are welded together at least at the points of intersection between the pores, in particular thermally welded, swell welded, cold-welded, ultrasonically welded and / or at least partially together
  • the porous film according to the invention has the advantage of a homogeneous structure and a good tensile strength in the longitudinal and in the transverse direction. Another advantage is that the claimed film can easily be wound up without the connections of the fibers at the crossover points impeding the winding up. When winding up this film neither break the individual fibers, nor the compounds at the crossover points.
  • the invention likewise relates to a process for the production of the porous film, which is characterized in that a woven or knitted fabric comprising or consisting of thermoplastic polymer fibers is compacted under a surface or line pressure at least once, the polymer fibers at least on the
  • Crossover points welded together in particular thermowelded, swell welded, cold-welded, ultrasonically welded, and / or at least partially fused together or non-positively or positively connected to each other. This is done at a surface or line pressure less than or equal to 500 N / mm, and a temperature less than or equal to 50% below the melting temperature of the lowest melting polymer.
  • the inventive method has the advantage that the macroscopic thickness of the resulting film can be adjusted, by continuously adjustable
  • the invention therefore also relates to the film obtained according to the method and the use of the film according to the invention or the invention obtained as a separator in batteries, as well as packaging material, membrane, filter, and as a carrier material for ceramic composite membranes.
  • One possible use of the film according to the invention is, for example, as a carrier of a ceramic coating in the production of ceramic separators, for example the SEPARION® separator, which is particularly suitable for use in high-performance lithium-ion batteries because of its temperature and chemical resistance.
  • the invention is therefore also a lithium-ion battery, the
  • the film according to the invention may have a thickness of less than or equal to 100 ⁇ m and / or an open area of greater than or equal to 20%. This makes them suitable for use as a separator in a battery. Particularly preferably, the film may have a thickness of less than or equal to 20 ⁇ m. This makes them suitable for use as a separator in a high-performance battery, particularly preferably in a lithium-ion battery.
  • the fibers of the film according to the invention may advantageously contain or consist of a plastic with a low melting point. An example of a partial
  • Melting polymer is polyethylene terephthalate (PET), which melts at 210 - 235 ° C.
  • PET polyethylene terephthalate
  • a preferred plastic may be Vestamelt®.
  • mixtures of fibers which can bring about fusion or fusion are advantageous, particularly preferably in the longitudinal direction of the polyester and in the transverse direction
  • polymer fibers of the film according to the invention may comprise or consist of at least one thermoplastic polymer. More preferably, the polymer of these fibers may be selected from polyacrylonitrile, polyester, polyamide, polyimide, polyaramid, polyolefins, PTFE, PVDF, PES, PUR, or a combination of these polymers.
  • polymer fibers of the film according to the invention may comprise or consist of at least one thermoplastic and at least one non-thermoplastic polymer, core-shell fibers, and / or co-extrudates.
  • polymer fibers of the film according to the invention comprise at least one thermoplastic and at least one non-thermoplastic polymer, these may be selected from core-shell fibers, wherein the core material comprises or is at least one non-thermoplastic polymer,
  • thermoplastic polymer fibers in warp direction and non-thermoplastic
  • thermoplastic polymer fibers in the warp direction and thermoplastic
  • Polymer fibers comprising or consisting of a finer thermoplastic and non-thermoplastic polymer fibers, or
  • the film according to the invention which comprises polymer fibers made of or with thermoplastic and non-thermoplastic polymer, has the advantage that the film according to the invention or obtained according to the invention has a greater tensile strength than a film which consists of an extruded polymer composition.
  • a particular advantage is that such a film calendering or further processing in roll-to-roll processes, for example
  • the film of the invention or obtained according to the invention with ceramic material can coat and subsequently heat treated, for example in the preparation of SEPARION ® separator.
  • the film has the advantage that its tensile strength can be adapted to the requirements of calendering, for example by selecting the non-thermoplastic polymer for the fibers in the warp direction.
  • the film has the advantage that very thin Films can be obtained by selecting particularly thin thermoplastic and / or non-thermoplastic polymer fibers.
  • thermosetting polymer fiber core also gives the film according to the invention more strength. Also, this selection affects the thickness of the porous film because the material does not deform so easily. Although the film according to the invention has a higher stability and thus a low deformability and a higher shear modulus, a less elastic behavior in the calendering gap is to be considered.
  • the polymer fibers may particularly preferably be coated fibers which are obtained by methods known to the person skilled in the art, for example the so-called
  • Bicomponent spins or coextrusion are particularly preferred.
  • Further preferred fibers may also be staple fibers as "spunbond” or very short and fine meltblown fibers available from Fare SpA, Via Pastrengo 31, Fagnono, Olona (VA), 21054, Italy.
  • the films according to the invention or those obtained according to the invention can be converted into ceramic composite membranes by coating with ceramic dispersions.
  • An example of the prior art is SEPARION ® in which a polymeric web is used instead of a perforated polymer film.
  • the further subject of the invention is a process for the preparation of
  • porous film according to the invention characterized in that a woven or knitted fabric comprising or consisting of thermoplastic polymer fibers, under a surface or line pressure of less than or equal to 500 N / mm, and a temperature less than or equal to 50% below the melting temperature of the lowest melting polymer is compressed at least once, wherein the polymer fibers at least to the
  • Crossover points welded together in particular thermowelded, source welded, cold-welded, ultrasound l-welded, and / or at least partially fused together or positively or non-positively connected to each other.
  • the woven or knitted fabric is continuously compressed in calenders or belt presses.
  • a line pressure of less than or equal to 500 N / mm is used.
  • plate presses are favored for a discontinuous procedure.
  • a temperature less than or equal to 10% below the melting temperature of the lowest melting polymer may be selected.
  • At least one additional calendering is the additional functionality, preferably by applying a further fabric or nonwoven.
  • a further fabric or nonwoven Preferably, an extremely thin aramid nonwoven can be calendered.
  • PET Polyethylene terephthalate
  • the tensile strengths were determined according to DIN EN ISO 527-1 in each case in the so-called “material direction” (MD) known to the person skilled in the art and in “cross direction” (CD). The results are shown in Table 1. At a line pressure of 300 N / mm, a transport speed of 10 m / min and a temperature of 220 ° C, a porous film according to the invention was obtained with a thickness of 14 ⁇ . The measured tensile strengths are shown in Table 1 in row 1. The tensile strengths of calendering the fabric in a line pressure of
  • Line 3 shows the tensile strengths of those obtained from the same fabric
  • Line 4 shows the tensile strengths of those obtained from the same fabric
  • PET films with thicknesses of 18 ⁇ or 1 1 ⁇ were perforated two-dimensionally with a laser. This area perforation can be performed with C02 lasers. The method is based on the one-dimensional perforation as it is performed, for example, at the companies Maag or Micro Laser Tech and u.a. in JP63023936 or JP1 1077872.
  • the resulting perforated films had an open area of 22% and 15%, respectively, summarized in lines 5 and 6 of Table 1, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cell Separators (AREA)
  • Nonwoven Fabrics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a foil which includes polymeric fibres, the polymeric fibres of which are interwelded, more particularly heat welded, solvent welded, cold welded, ultrasonically welded and/or at least partly interfused or positively or nonpositively interconnected at the crossing points between the pores at least, a process for production thereof, and also use thereof.

Description

Dünne, makroporöse Polymerfolien  Thin, macroporous polymer films
Die Erfindung betrifft eine Folie, die Polymerfasern aufweist, die zumindest an den The invention relates to a film comprising polymer fibers, at least to the
Überkreuzungspunkten zwischen den Poren miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschall-verschweißt und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden sind. Crossover points between the pores welded together, in particular thermowelded, swell-welded, cold-welded, ultrasonically welded and / or at least partially fused together or non-positively or positively connected to each other.
Unter einer Faser wird im Rahmen der vorliegenden Erfindung ein im Verhältnis zur Länge dünnes Gebilde verstanden, welches flexibel ist und keine Druck-, sondern nur Zugkräfte aufnehmen kann. Fasern knicken bei Druckbelastung. In Natur und Technik kommen Fasern meist in einem größeren Verbund vor, sie bilden eine bestimmte Struktur. Fasern sehr großer, praktisch unbegrenzter Länge heißen Filamente, Fasern begrenzter Länge Spinnfasern. In the context of the present invention, a fiber is understood to be a thin structure in relation to the length, which is flexible and can absorb no tensile forces but only tensile forces. Fibers buckle under pressure. In nature and technology fibers usually occur in a larger composite, they form a specific structure. Fibers of very large, virtually unlimited length are filaments, fibers of limited length are staple fibers.
Spinnfasern teilen sich wiederum in tatsächlich verspinnbare Stapelfasern und unter einer Grenzlänge von etwa 15 mm Flockfasern. Im Unterschied dazu ist ein Garn nach DIN 60900 ein Sammelbegriff für alle linienförmigen textilen Gebilde. Danach ist ein Garn sinngemäß ein langes, dünnes Gebilde aus einer oder mehreren Fasern. Es ist ein textiles Zwischenprodukt, welches zu Geweben, Gestricken, Gewirken und Stickereien verarbeitet werden kann oder auch zum Nähen verwendet wird. Staple fibers in turn divide into actually spinnable staple fibers and below a limit length of about 15 mm flock fibers. In contrast, a yarn according to DIN 60900 is a collective term for all linear textile structures. Thereafter, a yarn is analogous to a long, thin structure of one or more fibers. It is a textile intermediate that can be made into fabrics, crocheted, knitted and embroidered or used for sewing.
Poröse Folien werden üblicherweise erhalten, indem man Folien, z.B. Polymerfilme, perforiert oder deren ursprüngliche Struktur mechanisch oder chemisch schädigt. Derartige Materialien können unterschiedlichsten Verwendungen zugeführt werden, beispielsweise als Porous films are usually obtained by subjecting films, e.g. Polymer films, perforated or damage their original structure mechanically or chemically. Such materials can be supplied to a wide variety of uses, for example as
Verpackungsmaterialien, Trenn- und Filtrationsmembranen oder als Separatoren. Packaging materials, separation and filtration membranes or as separators.
Die deutsche Patentanmeldung DE 10 2009 047 440 offenbart Herstellung und Eigenschaften von dünnen, perforierten Folien, die für Beschichtungs- oder Imprägnierungsprozesse stabil sind. Die Folien enthalten oder sind aus Metall oder Polymer und werden mittels eines bei einer geeigneten Wellenlänge emittierenden Lasers perforiert. German patent application DE 10 2009 047 440 discloses production and properties of thin, perforated films which are stable for coating or impregnation processes. The films contain or are made of metal or polymer and are perforated by means of a laser emitting at a suitable wavelength.
Eine wichtige Größe, das durchbrochenes Material charakterisiert, ist die offene Fläche. Sie ist durch die Poren gegeben und wird bestimmt, indem man das Material als zweidimensionales Gebilde betrachtet und die von den Poren eingenommene Fläche ins Verhältnis zur gesamten von dem Material eingenommenen Fläche setzt. Sind die Poren regelmäßig angeordnet, lassen sich Elementarzellen finden, von denen man bei der Bestimmung der offenen Fläche ausgehen kann. Die Kantenlänge der Flächenstücke kann zum Beispiel gleich dem 100- fachen Porendurchmesser gewählt werden. An important variable that characterizes openwork material is the open area. It is given through the pores and is determined by considering the material as a two-dimensional structure and the area occupied by the pores in relation to the total set of the material occupied area. If the pores are arranged regularly, elementary cells can be found that can be used to determine the open area. The edge length of the patches can be selected, for example, equal to 100 times the pore diameter.
Eine weitere wichtige Größe, die für das Verarbeiten des durchbrochenen Materials von Bedeutung ist, ist die Zugfestigkeit, abgekürzt Fmax. Sie wird im Rahmen der Erfindung gemäß DIN EN ISO 527-1 bestimmt. Die Aufgabe der vorliegenden Erfindung besteht darin, ein alternatives durchbrochenes Material bereit zu stellen, dessen offene Fläche bei minimaler Dicke und guter Zugfestigkeit auf einfache Weise kontrolliert werden kann. Another important quantity of importance for processing the openwork material is the tensile strength, abbreviated F max . It is determined in the context of the invention according to DIN EN ISO 527-1. The object of the present invention is to provide an alternative perforated material whose open area can be easily controlled with minimum thickness and good tensile strength.
Es wurde gefunden, dass eine poröse Folie erhalten wird, indem ein Gewebe oder Gewirke, das Polymerfasern aufweist oder aus diesen besteht, derart verdichtet wird, dass die Fasern zumindest an ihren Überkreuzungspunkten miteinander verschweißt und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden sind. Nach einer solchen Behandlung haben die Fasern im Querschnitt ihre ursprüngliche Form verloren, sind aber, zum Beispiel unter lichtmikroskopischer Betrachtung, noch als solche erkennbar. Das makroskopische Gebilde dagegen hat nicht mehr die Eigenschaften eines herkömmlichen Gewebes oder Gewirkes - einzelne Fäden oder Fasern lassen sich nicht mehr abtrennen. It has been found that a porous film is obtained by densifying a woven or knitted fabric comprising or consisting of polymer fibers such that the fibers are welded together at least at their points of intersection and / or at least partly fused together or non-positively or positively connected to each other. After such treatment, the fibers have lost their original shape in cross-section, but are still recognizable as such, for example under light microscopic observation. By contrast, the macroscopic structure no longer has the properties of a conventional fabric or knitted fabric - individual threads or fibers can no longer be separated off.
Gegenstand der Erfindung ist also eine poröse Folie, welche dadurch gekennzeichnet ist, dass die Folie Polymerfasern aufweist, die zumindest an den Überkreuzungspunkten zwischen den Poren miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschall-verschweißt und/oder zumindest teilweise miteinander The invention thus relates to a porous film, which is characterized in that the film comprises polymer fibers which are welded together at least at the points of intersection between the pores, in particular thermally welded, swell welded, cold-welded, ultrasonically welded and / or at least partially together
verschmolzen oder kraft- oder formschlüssig miteinander verbunden sind. Die erfindungsgemäße poröse Folie hat den Vorteil einer homogenen Struktur sowie einer guten Zugfestigkeit in Längs- und in Querrichtung. Ein weiterer Vorteil besteht darin, dass sich die beanspruchte Folie leicht aufwickeln lässt, ohne dass die Verbindungen der Fasern an den Überkreuzungspunkten das Aufwickeln behindern. Beim Aufwickeln dieser Folie brechen außerdem weder die einzelnen Fasern, noch die Verbindungen an den Überkreuzungspunkten. fused or non-positively or positively connected with each other. The porous film according to the invention has the advantage of a homogeneous structure and a good tensile strength in the longitudinal and in the transverse direction. Another advantage is that the claimed film can easily be wound up without the connections of the fibers at the crossover points impeding the winding up. When winding up this film neither break the individual fibers, nor the compounds at the crossover points.
Ebenfalls Gegenstand der Erfindung ist ein Verfahren zur Herstellung der porösen Folie, welches dadurch gekennzeichnet ist, dass ein Gewebe oder Gewirke, das thermoplastische Polymerfasern aufweist oder aus diesen besteht, unter einem Flächen- oder Liniendruck zumindest einmal verdichtet wird, wobei die Polymerfasern zumindest an den The invention likewise relates to a process for the production of the porous film, which is characterized in that a woven or knitted fabric comprising or consisting of thermoplastic polymer fibers is compacted under a surface or line pressure at least once, the polymer fibers at least on the
Überkreuzungspunkten miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschall-verschweißt, und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden werden. Dies erfolgt bei einem Flächen- oder Liniendruck kleiner gleich 500 N/mm, und einer Temperatur kleiner gleich 50% unterhalb der Schmelztemperatur des am niedrigsten schmelzenden Polymers. Crossover points welded together, in particular thermowelded, swell welded, cold-welded, ultrasonically welded, and / or at least partially fused together or non-positively or positively connected to each other. This is done at a surface or line pressure less than or equal to 500 N / mm, and a temperature less than or equal to 50% below the melting temperature of the lowest melting polymer.
Das erfindungsgemäße Verfahren hat den Vorteil, dass die makroskopische Dicke der erhaltenen Folie eingestellt werden kann, und zwar durch kontinuierlich einstellbaren The inventive method has the advantage that the macroscopic thickness of the resulting film can be adjusted, by continuously adjustable
Liniendruck im Walzenspalt eines Kalanders oder einer Bandpresse beim Verdichten, sowie durch das Einstellen der Temperatur der Walzen. Weiterhin ist an dem erfindungsgemäßen Verfahren vorteilhaft, dass dünne Folien mit Dicken kleiner gleich 200 μηι, bevorzugt kleiner gleich 50 μηι, besonders bevorzugt extrem dünne Folien mit Dicken kleiner gleich 20 μηι erhalten werden. Mit Auswahl der Maschenweite und Fadenstärke, sowie der Bedingungen beim Verdichten, nämlich Liniendruck, Spaltweite und Temperatur werden auch die offene Fläche und die Lochgröße kontrolliert. Außerdem ist eine diskontinuierliche Folienfertigung unter den gleichen Einflussgrößen in Plattenpressen möglich. Diese Verfahren ermöglichen insbesondere die Verwendung derart hergestellter porösen Folie als eine Komponente des Separators in Hochleistungsbatterien, zum Beispiel als Träger einer keramischen Line pressure in the nip of a calender or a belt press during compression, and by adjusting the temperature of the rollers. Furthermore, it is advantageous in the process according to the invention that thin films having thicknesses of less than or equal to 200 μm, preferably less than or equal to 50 μm, particularly preferably extremely thin films having thicknesses of less than or equal to 20 μm, can be obtained. By selecting the mesh size and thread thickness, as well as the conditions of compression, namely line pressure, gap width and temperature, the open area and the hole size are controlled. In addition, a discontinuous film production under the same parameters in plate presses is possible. In particular, these methods make it possible to use such a porous film as a component of the separator in high-performance batteries, for example as a carrier for a ceramic
Beschichtung des Separators. Beispiele keramische Beschichtungen aufweisender Coating of the separator. Examples having ceramic coatings
Separatoren sind in den Patentanmeldungen DE 19741498, DE 1981 1708, DE 19812035, DE 19820580, DE 19824666, DE 10142622, DE 10208280, DE 10208277, DE 10238941 , DE 10238944, DE 10238945, DE 10240032, DE 10255121 , DE 10255122, DE 10347570, DE 10347569, DE 10347566, DE 10347568, DE 10347567, DE 10 2004 018929, DE 10 2004 018930, DE 10 2005 029124, DE 10 2005 042215, DE 10 2007 005156 Separators are described in the patent applications DE 19741498, DE 1981 1708, DE 19812035, DE 19820580, DE 19824666, DE 10142622, DE 10208280, DE 10208277, DE 10238941, DE 10238944, DE 10238945, DE 10240032, DE 10255121, DE 10255122, DE 10347570 DE 10347569, DE 10347566, DE 10347568, DE 10347567, DE 10 2004 018929, DE 10 2004 018930, DE 10 2005 029124, DE 10 2005 042215, DE 10 2007 005156
DE 10 2009 002680 beschrieben. DE 10 2009 002680.
Gegenstand der Erfindung ist deshalb auch die verfahrensgemäß erhaltene Folie und die Verwendung der erfindungsgemäßen oder erfindungsgemäß erhaltenen Folie als Separator in Batterien, außerdem als Verpackungsmaterial, Membran, Filter, und als Trägermaterial für keramische Kompositmembranen. The invention therefore also relates to the film obtained according to the method and the use of the film according to the invention or the invention obtained as a separator in batteries, as well as packaging material, membrane, filter, and as a carrier material for ceramic composite membranes.
Eine mögliche Verwendung der erfindungsgemäßen Folie ist beispielsweise als Träger einer keramischen Beschichtung bei der Herstellung keramischer Separatoren, zum Beispiel des SEPARION® Separators, der wegen seiner Temperatur- und Chemikalienbeständigkeit besonders für die Verwendung in hochleistungsfähigen Lithiumionen- Batterien geeignet ist. One possible use of the film according to the invention is, for example, as a carrier of a ceramic coating in the production of ceramic separators, for example the SEPARION® separator, which is particularly suitable for use in high-performance lithium-ion batteries because of its temperature and chemical resistance.
Gegenstand der Erfindung ist deshalb auch eine Lithiumionen- Batterie, die die The invention is therefore also a lithium-ion battery, the
erfindungsgemäße Folie als Separator aufweist. Has inventive film as a separator.
Die Erfindung wird im Folgenden näher erläutert. The invention will be explained in more detail below.
Die erfindungsgemäße Folie kann eine Dicke von kleiner oder gleich 100 μηι und/oder eine Offene Fläche von größer oder gleich 20 % aufweisen. Dies macht sie für den Einsatz als Separator in einer Batterie geeignet. Besonders bevorzugt kann die Folie eine Dicke von kleiner oder gleich 20 μηι aufweisen. Dies macht sie für den Einsatz als Separator in einer Hochleistungsbatterie, besonders bevorzugt in einer Lithiumionen-Batterie, geeignet. Die Fasern der erfindungsgemäßen Folie können vorteilhaft einen Kunststoff mit niedrigem Schmelzpunkt enthalten oder aus diesem bestehen. Ein Beispiel für ein teilweise The film according to the invention may have a thickness of less than or equal to 100 μm and / or an open area of greater than or equal to 20%. This makes them suitable for use as a separator in a battery. Particularly preferably, the film may have a thickness of less than or equal to 20 μm. This makes them suitable for use as a separator in a high-performance battery, particularly preferably in a lithium-ion battery. The fibers of the film according to the invention may advantageously contain or consist of a plastic with a low melting point. An example of a partial
schmelzendes Polymer ist Polyethylenterephthalat (PET), das bei 210 - 235 °C schmilzt. Ein bevorzugter Kunststoff kann Vestamelt® sein. In einer weiteren Ausführung der Erfindung sind Mischungen von Fasern vorteilhaft, die das Verschweißen bzw. Verschmelzen bewirken können, besonders bevorzugt in Längsrichtung Polyester- und in Querrichtung Melting polymer is polyethylene terephthalate (PET), which melts at 210 - 235 ° C. A preferred plastic may be Vestamelt®. In a further embodiment of the invention, mixtures of fibers which can bring about fusion or fusion are advantageous, particularly preferably in the longitudinal direction of the polyester and in the transverse direction
Polyolefinfasern. Die Polymerfasern der erfindungsgemäßen Folie können zumindest ein thermoplastisches Polymer aufweisen oder daraus bestehen. Besonders bevorzugt kann das Polymer dieser Fasern ausgewählt sein aus Polyacrylnitril, Polyester, Polyamid, Polyimid, Polyaramid, Polyolefinen, PTFE, PVDF, PES, PUR, oder eine Kombination dieser Polymere. Polyolefin fibers. The polymer fibers of the film according to the invention may comprise or consist of at least one thermoplastic polymer. More preferably, the polymer of these fibers may be selected from polyacrylonitrile, polyester, polyamide, polyimide, polyaramid, polyolefins, PTFE, PVDF, PES, PUR, or a combination of these polymers.
Weiterhin besonders bevorzugt können die Polymerfasern der erfindungsgemäßen Folie zumindest ein thermoplastisches und zumindest ein nicht-thermoplastisches Polymer, Core- Shell Fasern, und/oder Coextrudate aufweisen oder daraus bestehen. With particular preference the polymer fibers of the film according to the invention may comprise or consist of at least one thermoplastic and at least one non-thermoplastic polymer, core-shell fibers, and / or co-extrudates.
Falls die Polymerfasern der erfindungsgemäßen Folie zumindest ein thermoplastisches und zumindest ein nicht-thermoplastisches Polymer aufweisen, können diese ausgewählt sein aus Core-Shell-Fasern, wobei das Kernmaterial zumindest ein nicht-thermoplastisches Polymer aufweist oder ist, If the polymer fibers of the film according to the invention comprise at least one thermoplastic and at least one non-thermoplastic polymer, these may be selected from core-shell fibers, wherein the core material comprises or is at least one non-thermoplastic polymer,
coextrudierte Fasern,  coextruded fibers,
thermoplastische Polymerfasern in Kett-Richtung und nicht-thermoplastische  thermoplastic polymer fibers in warp direction and non-thermoplastic
Polymerfasern in Schussrichtung,  Polymer fibers in weft direction,
nicht-thermoplastische Polymerfasern in Kett-Richtung und thermoplastische  non-thermoplastic polymer fibers in the warp direction and thermoplastic
Polymerfasern in Schussrichtung,  Polymer fibers in weft direction,
Polymerfasern, die feinere thermoplastische und nicht-thermoplastische Polymerfasern aufweisen oder aus einem solchen Fasergemisch bestehen, oder  Polymer fibers comprising or consisting of a finer thermoplastic and non-thermoplastic polymer fibers, or
eine Kombination aus diesen Fasern sein. a combination of these fibers.
Die erfindungsgemäße Folie, die Polymerfasern aus oder mit thermoplastischem und nichtthermoplastischem Polymer aufweist, hat den Vorteil, dass die erfindungsgemäße oder erfindungsgemäß erhaltene Folie eine größere Zugfestigkeit aufweist, als eine Folie, die aus einer extrudierten Polymermasse besteht. Besonderer Vorteil ist, dass sich eine solche Folie kalandrieren oder in Rolle-zu-Rolle Prozessen weiter bearbeiten, zum Beispiel The film according to the invention, which comprises polymer fibers made of or with thermoplastic and non-thermoplastic polymer, has the advantage that the film according to the invention or obtained according to the invention has a greater tensile strength than a film which consists of an extruded polymer composition. A particular advantage is that such a film calendering or further processing in roll-to-roll processes, for example
wärmebehandeln lässt. Ganz besonderer Vorteil ist, dass sich die erfindungsgemäße oder erfindungsgemäß erhaltene Folie mit keramischem Material beschichten und anschließend wärmebehandeln lässt, zum Beispiel bei der Herstellung des SEPARION® Separators. Des Weiteren hat die Folie den Vorteil, dass sich ihre Zugfestigkeit an die Erfordernisse des Kalandrierens anpassen lässt, indem man z.B. das nicht-thermoplastische Polymer für die Fasern in Kett-Richtung auswählt. Außerdem hat die Folie den Vorteil, dass besonders dünne Folien erhalten werden können, indem man besonders dünne thermoplastische und/oder nicht-thermoplastische Polymerfasern auswählt. heat treatable. Is quite special advantage that the film of the invention or obtained according to the invention with ceramic material can coat and subsequently heat treated, for example in the preparation of SEPARION ® separator. Furthermore, the film has the advantage that its tensile strength can be adapted to the requirements of calendering, for example by selecting the non-thermoplastic polymer for the fibers in the warp direction. In addition, the film has the advantage that very thin Films can be obtained by selecting particularly thin thermoplastic and / or non-thermoplastic polymer fibers.
Ein duroplastischer Polymerfaserkern verleiht der erfindungsgemäßen Folie überdies mehr Festigkeit. Auch beeinflusst diese Auswahl die Dicke der porösen Folie, da sich das Material nicht so leicht verformt. Die erfindungsgemäße Folie weist zwar eine höhere Stabilität und somit eine geringe Verformbarkeit und ein höheres Schubmodul auf, doch ist ein weniger elastisches Verhalten im Kalanderspalt zu beachten. Besonders bevorzugt können die Polymerfasern ummantelte Fasern sein, die mittels dem Fachmann bekannter Verfahren erhalten werden, zum Beispiel dem sogenannten A thermosetting polymer fiber core also gives the film according to the invention more strength. Also, this selection affects the thickness of the porous film because the material does not deform so easily. Although the film according to the invention has a higher stability and thus a low deformability and a higher shear modulus, a less elastic behavior in the calendering gap is to be considered. The polymer fibers may particularly preferably be coated fibers which are obtained by methods known to the person skilled in the art, for example the so-called
Bicomponentenspinnen oder der Coextrusion. Unter der Vielzahl ummantelter Fasern können zum Beispiel solche mit einem PET-Kern, ummantelt mit PA, besonders bevorzugt sein. Weiterhin bevorzugte Fasern können auch Stapelfasern als„Spunbond" oder sehr kurze und feine Meltblown-Fasern sein, die bei der Firma Fare SpA, Via Pastrengo 31, Fagnono, Olona (VA), 21054, Italy, erhältlich sind. Bicomponent spins or coextrusion. Among the plurality of coated fibers, for example, those having a PET core coated with PA may be particularly preferred. Further preferred fibers may also be staple fibers as "spunbond" or very short and fine meltblown fibers available from Fare SpA, Via Pastrengo 31, Fagnono, Olona (VA), 21054, Italy.
Es ist außer dem zuvor Gesagten jede weitere dem Fachmann für Textilien bekannte It is beyond the foregoing any further known to the skilled textiles expert
Kombination an Fasern und Polymeren möglich. Combination on fibers and polymers possible.
Des Weiteren können die erfindungsgemäßen bzw. erfindungemäß erhaltenen Folien durch Beschichtung mit keramischen Dispersionen in keramische Kompositmembranen überführt werden. Ein Beispiel des Standes der Technik ist SEPARION®, worin ein Polymervlies an Stelle eines perforierten Polymerfilmes verwendet wird. Furthermore, the films according to the invention or those obtained according to the invention can be converted into ceramic composite membranes by coating with ceramic dispersions. An example of the prior art is SEPARION ® in which a polymeric web is used instead of a perforated polymer film.
Der weitere Gegenstand der Erfindung ist ein Verfahren zur Herstellung der The further subject of the invention is a process for the preparation of
erfindungsgemäßen porösen Folie, welches dadurch gekennzeichnet ist, dass ein Gewebe oder Gewirke, das thermoplastische Polymerfasern aufweist oder aus diesen besteht, unter einem Flächen- oder Liniendruck kleiner gleich 500 N/mm, und einer Temperatur kleiner gleich 50% unterhalb der Schmelztemperatur des am niedrigsten schmelzenden Polymers zumindest einmal verdichtet wird, wobei die Polymerfasern zumindest an den porous film according to the invention, characterized in that a woven or knitted fabric comprising or consisting of thermoplastic polymer fibers, under a surface or line pressure of less than or equal to 500 N / mm, and a temperature less than or equal to 50% below the melting temperature of the lowest melting polymer is compressed at least once, wherein the polymer fibers at least to the
Überkreuzungspunkten miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschal l-verschweißt, und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden werden. Crossover points welded together, in particular thermowelded, source welded, cold-welded, ultrasound l-welded, and / or at least partially fused together or positively or non-positively connected to each other.
Bevorzugt wird das Gewebe oder Gewirke kontinuierlich in Kalandern oder Bandpressen verdichtet. Vorzugsweise wird ein Liniendruck kleiner gleich 500 N/mm eingesetzt. Weiterhin favorisiert werden für eine diskontinuierliche Verfahrensweise Plattenpressen. Ebenso bevorzugt kann eine Temperatur kleiner oder gleich 10 % unterhalb der Schmelztemperatur des am niedrigsten schmelzenden Polymers gewählt werden. In dem erfindungsgemäßen Verfahren kann es vorteilhaft sein, das Gewebe oder Gewirke zumindest zweimal zu verdichten, wobei sich jedes weitere Verdichten von dem Preferably, the woven or knitted fabric is continuously compressed in calenders or belt presses. Preferably, a line pressure of less than or equal to 500 N / mm is used. Furthermore, plate presses are favored for a discontinuous procedure. Also preferably, a temperature less than or equal to 10% below the melting temperature of the lowest melting polymer may be selected. In the method according to the invention, it may be advantageous to compress the fabric or knit at least twice, with each further densification of the
vorhergehenden Verdichten in dem Liniendruck, der Spaltbreite, und/oder der Temperatur unterscheidet. Die Herstellung der Gewebe und Gewirke erfolgt gemäß dem Stand der Technik, zum Beispiel bei den Firmen Andritz in Krefeld, Webatex in Bayreuth oder Sefar Schweiz, sowie die erfindungsgemäße Weiterverarbeitung mittels eines Kalanders. previous densities in line pressure, gap width, and / or temperature. The production of the woven and knitted fabric is carried out according to the state of the art, for example at the companies Andritz in Krefeld, Webatex in Bayreuth or Sefar Switzerland, as well as the further processing according to the invention by means of a calender.
Vorteil zumindest eines weiteren Kalandrierens ist die zusätzliche Funktionalität, vorzugsweise durch Aufbringung eines weiteren Gewebes oder Vlieses. Bevorzugt kann ein extrem dünnes Aramidvlies aufkalandriert werden. Advantage of at least one additional calendering is the additional functionality, preferably by applying a further fabric or nonwoven. Preferably, an extremely thin aramid nonwoven can be calendered.
Beispiele 1 bis 4. Examples 1 to 4.
Polyethylenterephthalat (PET) Gewebe mit 10 dtex, entsprechend monofil 27 μηι,  Polyethylene terephthalate (PET) fabric with 10 dtex, corresponding to monofilament 27 μηι,
Maschenweite 135 μηι und einer Dicke von 44 μηι, gezeigt in Abbildung 1 , wurde unter verschiedenen Liniendrücken, Temperaturen und Transportgeschwindigkeiten kalandriert. Mesh size 135 μηι and a thickness of 44 μηι, shown in Figure 1, was calendered under different line pressures, temperatures and transport speeds.
Die Zugfestigkeiten wurden gemäß DIN EN ISO 527-1 jeweils in der dem Fachmann bekannten sogenannten„material direction" (MD) und in„cross direction" (CD) bestimmt. Die Ergebnisse zeigt die Tabelle 1. Bei einem Liniendruck von 300 N/mm, einer Transportgeschwindigkeit von 10 m/min und einer Temperatur von 220 °C wurde eine erfindungsgemäße poröse Folie mit einer Dicke von 14 μηι erhalten. Die gemessenen Zugfestigkeiten zeigt Tabelle 1 in Zeile 1. Die Zugfestigkeiten der beim Kalandrieren des Gewebes bei einem Liniendruck von The tensile strengths were determined according to DIN EN ISO 527-1 in each case in the so-called "material direction" (MD) known to the person skilled in the art and in "cross direction" (CD). The results are shown in Table 1. At a line pressure of 300 N / mm, a transport speed of 10 m / min and a temperature of 220 ° C, a porous film according to the invention was obtained with a thickness of 14 μηι. The measured tensile strengths are shown in Table 1 in row 1. The tensile strengths of calendering the fabric in a line pressure of
150 N/mm, einer Transportgeschwindigkeit von 3 m/min, und einer Temperatur von 210 °C erhaltenen erfindungsgemäßen Folie sind in Zeile 2 festgehalten.  150 N / mm, a transport speed of 3 m / min, and a temperature of 210 ° C obtained film according to the invention are recorded in line 2.
Zeile 3 zeigt die Zugfestigkeiten der aus dem gleichen Gewebe erhaltenen Line 3 shows the tensile strengths of those obtained from the same fabric
erfindungsgemäßen Folie beim Liniendruck von 250 N/mm, einer Transportgeschwindigkeit von 3 m/min, und einer Temperatur von 210 °C. Diese Folie ist gezeigt in Abbildung 2. film according to the invention at a line pressure of 250 N / mm, a transport speed of 3 m / min, and a temperature of 210 ° C. This slide is shown in Figure 2.
Zeile 4 zeigt die Zugfestigkeiten der aus dem gleichen Gewebe erhaltenen Line 4 shows the tensile strengths of those obtained from the same fabric
erfindungsgemäßen Folie beim Liniendruck von 300 N/mm, einer Transportgeschwindigkeit von 3 m/min, und einer Temperatur von 210 °C. film according to the invention at a line pressure of 300 N / mm, a transport speed of 3 m / min, and a temperature of 210 ° C.
Vergleichsbeispiele 5 und 6. Comparative Examples 5 and 6.
Handelsübliche PET Folien mit Dicken von 18 μηι bzw. 1 1 μηι wurden mit einem Laser zweidimensional perforiert. Diese flächige Perforation kann mit C02 Lasern durchgeführt werden. Das Verfahren ist angelehnt an die eindimensionale Perforation wie sie bspw. bei den Firmen Maag oder Micro Laser Tech durchgeführt wird und u.a. in den Schriften JP63023936 oder JP1 1077872 offenbart ist.  Commercially available PET films with thicknesses of 18 μηι or 1 1 μηι were perforated two-dimensionally with a laser. This area perforation can be performed with C02 lasers. The method is based on the one-dimensional perforation as it is performed, for example, at the companies Maag or Micro Laser Tech and u.a. in JP63023936 or JP1 1077872.
Die resultierenden perforierten Folien wiesen eine Offene Fläche von 22 % bzw. 15 % auf, zusammengefasst in den Zeilen 5 bzw. 6 der Tabelle 1. The resulting perforated films had an open area of 22% and 15%, respectively, summarized in lines 5 and 6 of Table 1, respectively.
Die Messung der CD Zugfestigkeit der 1 1 μηι dicken perforierten Folie, Pos. 6, scheiterte, da die Messbereichsuntergrenze unterschritten wurde. Muster Dicke Offene Zugfestigkeit The measurement of CD tensile strength of 1 1 μηι thick perforated film, pos. 6, failed because the lower limit of the measurement range was exceeded. Pattern Thickness Open Tensile Strength
(Mm) Fläche Fmax  (Mm) Area Fmax
(%)  (%)
MD CD  MD CD
(N/cm) (N/cm) (N / cm) (N / cm)
Beispiel example
Erfindungsgemäße  invention
1. 14 34 14 14 poröse Folie  1. 14 34 14 14 porous film
Erfindungsgemäße  invention
2. 18 28 8 8 poröse Folie  2. 18 28 8 8 porous film
Erfindungsgemäße  invention
3. 12 21 5 5 poröse Folie  3. 12 21 5 5 porous film
Erfindungsgemäße  invention
4. 10 23 5 5 poröse Folie  4. 10 23 5 5 porous film
5. Perforierte PET-Folie 18 22 4 35. Perforated PET film 18 22 4 3
6. Perforierte PET-Folie 1 1 15 4 6. Perforated PET film 1 1 15 4
Tabelle 1. Table 1.

Claims

Patentansprüche: claims:
1. Poröse Folie, 1. porous film,
dadurch gekennzeichnet,  characterized,
dass die Folie Polymerfasern aufweist, die zumindest an den Überkreuzungspunkten zwischen den Poren miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschall-verschweißt und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden sind.  the film comprises polymer fibers which are welded together, at least at the points of intersection between the pores, in particular thermally welded, swell-welded, cold-welded, ultrasonically welded and / or at least partially fused together or non-positively or positively connected with each other.
2. Folie gemäß Anspruch 1 , 2. A film according to claim 1,
die eine Dicke von kleiner oder gleich 100 μηι, bevorzugt 50 μηι, besonders bevorzugt kleiner gleich 20 μηι und/oder eine Offene Fläche von größer oder gleich 20 % aufweist.  having a thickness of less than or equal to 100 μηι, preferably 50 μηι, more preferably less than or equal to 20 μηι and / or has an open area of greater than or equal to 20%.
3. Folie nach Anspruch 1 oder 2, 3. A film according to claim 1 or 2,
dadurch gekennzeichnet,  characterized,
dass die Polymerfasern zumindest ein thermoplastisches Polymer aufweisen oder daraus bestehen.  the polymer fibers comprise or consist of at least one thermoplastic polymer.
4. Folie nach Anspruch 3, 4. A film according to claim 3,
dadurch gekennzeichnet,  characterized,
dass das Polymer der Fasern ausgewählt ist aus Polyacrylnitril, Polyester, Polyamid, Polyimid, Polyaramid, Polyolefin, PTFE, PVDF, PES, PUR, oder eine Kombination dieser Polymere.  the polymer of the fibers is selected from polyacrylonitrile, polyester, polyamide, polyimide, polyaramid, polyolefin, PTFE, PVDF, PES, PUR, or a combination of these polymers.
5. Folie nach zumindest einem der Ansprüche 1 bis 3, 5. A film according to at least one of claims 1 to 3,
dadurch gekennzeichnet,  characterized,
dass die Polymerfasern zumindest ein thermoplastisches und zumindest ein nichtthermoplastisches Polymer, Core-Shell Fasern, und/oder Coextrudate aufweisen oder daraus bestehen.  the polymer fibers comprise or consist of at least one thermoplastic and at least one non-thermoplastic polymer, core-shell fibers, and / or co-extrudates.
6. Verfahren zur Herstellung einer porösen Folie gemäß zumindest einem der 6. A process for producing a porous film according to at least one of
vorhergehenden Ansprüche, dadurch gekennzeichnet,  preceding claims, characterized
dass ein Gewebe oder Gewirke, das thermoplastische Polymerfasern aufweist oder aus diesen besteht, unter einem Flächen- oder Liniendruck kleiner gleich 500 N/mm, und einer Temperatur kleiner gleich 50% unterhalb der Schmelztemperatur des am niedrigsten schmelzenden Polymers that a woven or knitted fabric comprising or comprising thermoplastic polymer fibers this is, under a surface or line pressure less than or equal to 500 N / mm, and a temperature equal to or less than 50% below the melting temperature of the lowest-melting polymer
zumindest einmal verdichtet wird, wobei die Polymerfasern zumindest an den  is compressed at least once, wherein the polymer fibers at least to the
Überkreuzungspunkten miteinander verschweißt, insbesondere thermoverschweißt, quellverschweißt, kaltverschweißt, ultraschall-verschweißt, und/oder zumindest teilweise miteinander verschmolzen oder kraft- oder formschlüssig miteinander verbunden werden.  Crossover points welded together, in particular thermowelded, swell welded, cold-welded, ultrasonically welded, and / or at least partially fused together or non-positively or positively connected to each other.
7. Verfahren nach Anspruch 6, 7. The method according to claim 6,
dadurch gekennzeichnet,  characterized,
dass das Gewebe oder Gewirke zumindest zweimal verdichtet wird, wobei  that the woven or knitted fabric is compacted at least twice, wherein
sich jedes weitere Verdichten von dem vorhergehenden Verdichten  each further compacting from the previous compacting
in dem Liniendruck, der Spaltbreite, und/oder der Temperatur unterscheidet.  in the line pressure, the gap width, and / or the temperature is different.
8. Poröse Folie, erhalten nach zumindest einem der Ansprüche 6 oder 7. 8. Porous film obtained according to at least one of claims 6 or 7.
9. Verwendung der porösen Folie gemäß zumindest einem der Ansprüche 1 bis 8 als Separator in Batterien, Verpackungsmaterial, Membran, Trägermaterial für keramische Kompositmembranen, Filter. 9. Use of the porous film according to at least one of claims 1 to 8 as a separator in batteries, packaging material, membrane, carrier material for ceramic composite membranes, filters.
10. Lithiumionen-Batterie, einen Separator gemäß zumindest einem der Ansprüche 1 bis 8 aufweisend. 10. A lithium ion battery comprising a separator according to at least one of claims 1 to 8.
EP11805844.5A 2011-01-26 2011-12-22 Thin macroporous polymer films Withdrawn EP2668328A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011003186A DE102011003186A1 (en) 2011-01-26 2011-01-26 Thin, macroporous polymer films
PCT/EP2011/073799 WO2012100889A1 (en) 2011-01-26 2011-12-22 Thin macroporous polymer films

Publications (1)

Publication Number Publication Date
EP2668328A1 true EP2668328A1 (en) 2013-12-04

Family

ID=45464541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11805844.5A Withdrawn EP2668328A1 (en) 2011-01-26 2011-12-22 Thin macroporous polymer films

Country Status (7)

Country Link
US (1) US20130302695A1 (en)
EP (1) EP2668328A1 (en)
JP (1) JP2014505147A (en)
KR (1) KR20140006843A (en)
CN (1) CN103354848A (en)
DE (1) DE102011003186A1 (en)
WO (1) WO2012100889A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013200722A1 (en) 2012-01-30 2013-08-01 Evonik Litarion Gmbh Separator containing an organic-inorganic adhesion promoter component
KR101705305B1 (en) * 2012-10-22 2017-02-09 주식회사 엘지화학 Porous separator having uniform pore configuration and secondary battery comprising the same
CN103306014B (en) * 2013-07-05 2017-02-08 昆山豪绅纤维科技开发有限公司 Luminous fabric
DE102016114319B4 (en) * 2016-08-03 2019-02-28 Inteca Gmbh Flat lighting device
US11362338B2 (en) 2017-02-14 2022-06-14 Volkswagen Ag Electric vehicle battery cell with solid state electrolyte
US10797284B2 (en) 2017-02-14 2020-10-06 Volkswagen Ag Electric vehicle battery cell with polymer frame for battery cell components
US11870028B2 (en) 2017-02-14 2024-01-09 Volkswagen Ag Electric vehicle battery cell with internal series connection stacking
US11362371B2 (en) 2017-02-14 2022-06-14 Volkswagen Ag Method for manufacturing electric vehicle battery cells with polymer frame support
DE102017205653A1 (en) 2017-04-03 2018-10-04 Vitrulan Textile Glass Gmbh Glass-based battery separator
DE102017007858A1 (en) 2017-04-03 2018-10-04 Thorsten Gerdes Method for direct application of glass-based separators to battery electrodes
JP7067220B2 (en) 2018-04-11 2022-05-16 トヨタ自動車株式会社 Separator
WO2019242016A1 (en) * 2018-06-22 2019-12-26 Shanghai Energy New Materials Technology Co., Ltd. Separators, electrochemical devices comprising separators, and methods for making separators
CN114784462B (en) * 2022-04-14 2024-06-28 中材锂膜(常德)有限公司 Preparation method of isolating film
CN115101888B (en) * 2022-06-16 2024-03-26 广东工业大学 Multistage Kong Qianwei cloth-based polymer composite membrane and preparation method and application thereof
CN115874351A (en) * 2022-12-12 2023-03-31 江苏亨通精密铜业有限公司 Non-woven composite foil, preparation process and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB597514A (en) * 1943-12-08 1948-01-28 Sylvania Ind Corp Potentially adhesive filaments and yarns, fabrics, felts and similar textile materials made therewith
DE1010230B (en) * 1952-07-12 1957-06-13 Minnesota Mining & Mfg Artificial silk product, especially in ribbon form
CH345627A (en) * 1954-09-30 1960-04-15 Kimberly Clark Co Unwoven network and its uses
JP2005268096A (en) * 2004-03-19 2005-09-29 Tomoegawa Paper Co Ltd Separator for electronic component and manufacturing method thereof
JP2006144158A (en) * 2004-11-18 2006-06-08 Japan Vilene Co Ltd Nonwoven fabric, separator for electric double layer capacitor, separator for lithium-ion secondary battery, electric double layer capacitor and lithium-ion secondary battery
WO2008130391A2 (en) * 2006-11-29 2008-10-30 E. I. Du Pont De Nemours And Company Multiaxial polyethylene fabric and laminate

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2440846C2 (en) * 1974-08-26 1982-11-25 Gebr. Holzapfel & Co KG, 3446 Meinhard Openwork visual and / or sun protection membrane
US4068047A (en) * 1976-12-10 1978-01-10 The Kendall Company Flat-pack battery separator
US4169003A (en) * 1976-12-10 1979-09-25 The Kendall Company Flat-pack battery separator
JPS6323936A (en) 1986-07-17 1988-02-01 Dainippon Printing Co Ltd Production of perforated film
GB9403911D0 (en) * 1994-03-01 1994-04-20 Univ Manchester Porous films
GB2289688B (en) * 1994-05-27 1998-11-11 Fibertech Group Inc Articles and methods for sorbing,filtering and disposing of fluid waste
US5972808A (en) * 1997-01-30 1999-10-26 Aqf Technologies Llc Fibrous structures with fine particles
JP3405143B2 (en) 1997-09-17 2003-05-12 凸版印刷株式会社 Easy-cut laminated film packaging
DE19741498B4 (en) 1997-09-20 2008-07-03 Evonik Degussa Gmbh Production of a ceramic stainless steel mesh composite
DE19811708B4 (en) 1997-09-20 2008-09-04 Evonik Degussa Gmbh Production of ceramic membranes
US6103172A (en) * 1998-04-07 2000-08-15 Pall Corporation Method of preparaing a porous polytetrafluoroethylene membranne
JP3717782B2 (en) * 1999-12-24 2005-11-16 日本バイリーン株式会社 Electric double layer capacitor separator
JP3845536B2 (en) * 1999-12-24 2006-11-15 日本バイリーン株式会社 Manufacturing method of electric double layer capacitor
JP2001319635A (en) * 2000-05-12 2001-11-16 Matsushita Electric Ind Co Ltd Separator and its manufacturing method and nonaqueous battery using the same
DE10142622A1 (en) 2001-08-31 2003-03-20 Creavis Tech & Innovation Gmbh Electrical separator, process for its production and use
JP4052372B2 (en) * 2001-09-21 2008-02-27 日本板硝子株式会社 Sealed lead-acid battery separator and sealed lead-acid battery using the same
DE10208280A1 (en) 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Ceramic membrane based on a polymer or natural fiber substrate, process for its production and use
DE10208277A1 (en) 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Electrical separator, process for its production and use
DE10238941B4 (en) 2002-08-24 2013-03-28 Evonik Degussa Gmbh Electric separator, process for its manufacture and use in lithium high-performance batteries and a battery having the separator
DE10238944A1 (en) 2002-08-24 2004-03-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separator for use in high energy batteries and process for its manufacture
DE10238945B4 (en) 2002-08-24 2013-01-03 Evonik Degussa Gmbh Electric separator with shut-off mechanism, process for its preparation, use of the separator in lithium batteries and battery with the separator
DE10240032A1 (en) 2002-08-27 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Ion-conducting battery separator for lithium batteries, process for their production and their use
DE10255122A1 (en) 2002-11-26 2004-06-03 Creavis Gesellschaft Für Technologie Und Innovation Mbh Long-term stable separator for an electrochemical cell
DE10255121B4 (en) 2002-11-26 2017-09-14 Evonik Degussa Gmbh Separator with asymmetric pore structure for an electrochemical cell
DE10304734A1 (en) * 2002-12-18 2004-07-08 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separator comprising non-conductive polymer fibers with porous inorganic coating, useful in electrochemical cells, especially lithium batteries, where the polymer includes silicon-oxygen clusters
AU2004252862B2 (en) * 2003-06-09 2008-04-17 Saint-Gobain Ceramics & Plastics, Inc. Stack supported solid oxide fuel cell
DE10347569A1 (en) * 2003-10-14 2005-06-02 Degussa Ag Ceramic, flexible membrane with improved adhesion of the ceramic on the carrier fleece
DE10347566A1 (en) 2003-10-14 2005-05-12 Degussa Ceramic separator for electrochemical cells with improved conductivity
DE10347568A1 (en) 2003-10-14 2005-05-12 Degussa Capacitor with ceramic separation layer
DE10347570B4 (en) 2003-10-14 2015-07-23 Evonik Degussa Gmbh Inorganic separator-electrode unit for lithium-ion batteries, method for their production, use in lithium batteries and lithium batteries with the inorganic separator-electrode unit
DE10347567A1 (en) * 2003-10-14 2005-05-12 Degussa Electric separator with shut-off mechanism, process for its manufacture and use in lithium batteries
JP2005167042A (en) * 2003-12-04 2005-06-23 Furukawa Electric Co Ltd:The Adhesive tape for fixing semiconductor wafer
DE102004018929A1 (en) 2004-04-20 2005-11-17 Degussa Ag Electrolyte composition and its use as electrolyte material for electrochemical energy storage systems
DE102004018930A1 (en) 2004-04-20 2005-11-17 Degussa Ag Use of a ceramic separator in lithium-ion batteries having an electrolyte containing ionic liquids
JP4956961B2 (en) * 2004-12-22 2012-06-20 旭硝子株式会社 ELECTROLYTE MEMBRANE, METHOD FOR PRODUCING THE SAME, AND MEMBRANE ELECTRODE ASSEMBLY FOR SOLID POLYMER FUEL CELL
DE102005029124A1 (en) 2005-06-23 2006-12-28 Degussa Ag Electrolyte/separator system, useful for producing electro-chemical energy-storage systems e.g. lithium metal batteries, comprises electrolytes comprising base component, ionic liquid, water, additive, lead salt and ceramic separator
DE102005042215A1 (en) 2005-09-05 2007-03-08 Degussa Ag Separator with improved handling
US7112389B1 (en) * 2005-09-30 2006-09-26 E. I. Du Pont De Nemours And Company Batteries including improved fine fiber separators
DE102007005156A1 (en) * 2007-01-29 2008-08-14 Evonik Degussa Gmbh Ceramic membrane with improved adhesion to plasma-treated polymeric support material, as well as their preparation and use
WO2008120442A1 (en) * 2007-03-29 2008-10-09 Panasonic Corporation Positive electrode for rechargeable battery with nonaqueous electrolyte, and rechargeable battery with nonaqueous electrolyte
KR20100014725A (en) * 2007-04-05 2010-02-10 미쓰비시 가가꾸 가부시키가이샤 Nonaqueous electrolyte for rechargeable battery, and rechargeable battery with nonaqueous electrolyte
US9048508B2 (en) * 2007-04-20 2015-06-02 Mitsubishi Chemical Corporation Nonaqueous electrolytes and nonaqueous-electrolyte secondary batteries employing the same
TWI466370B (en) * 2008-01-17 2014-12-21 A123 Systems Inc Mixed metal olivine electrode materials for lithium ion batteries
US20090286147A1 (en) * 2008-05-16 2009-11-19 Atsushi Nakajima Composite porous membrane, method of producing composite porous membrane, and battery separator, battery and capacitor using the same
DE102008040896A1 (en) * 2008-07-31 2010-02-04 Evonik Degussa Gmbh Use of ceramic or ceramic-containing cutting or punching tools as cutting or punching for ceramic-containing composites
CN101392433B (en) * 2008-10-30 2010-06-23 王常义 Method for producing nonwoven gridding reinforced composite nonwoven fabrics
JP2010118315A (en) * 2008-11-14 2010-05-27 Toshiba Corp Nonaqueous electrolyte battery
JP2010123287A (en) * 2008-11-17 2010-06-03 Panasonic Corp Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery
DE102009002680A1 (en) 2009-04-28 2010-11-04 Evonik Litarion Gmbh Production and use of ceramic composite materials based on polymer carrier film
JP5337599B2 (en) * 2009-06-29 2013-11-06 ダイワボウホールディングス株式会社 Battery separator, battery and split type composite fiber
WO2011025823A1 (en) * 2009-08-25 2011-03-03 A123 Systems, Inc. Mixed metal olivine electrode materials for lithium ion batteries having improved specific capacity and energy density
DE102010001702A1 (en) 2009-12-03 2011-06-09 Evonik Degussa Gmbh Perforated foil
US9172075B2 (en) * 2010-12-21 2015-10-27 GM Global Technology Operations LLC Battery separators with variable porosity

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB597514A (en) * 1943-12-08 1948-01-28 Sylvania Ind Corp Potentially adhesive filaments and yarns, fabrics, felts and similar textile materials made therewith
DE1010230B (en) * 1952-07-12 1957-06-13 Minnesota Mining & Mfg Artificial silk product, especially in ribbon form
CH345627A (en) * 1954-09-30 1960-04-15 Kimberly Clark Co Unwoven network and its uses
JP2005268096A (en) * 2004-03-19 2005-09-29 Tomoegawa Paper Co Ltd Separator for electronic component and manufacturing method thereof
JP2006144158A (en) * 2004-11-18 2006-06-08 Japan Vilene Co Ltd Nonwoven fabric, separator for electric double layer capacitor, separator for lithium-ion secondary battery, electric double layer capacitor and lithium-ion secondary battery
WO2008130391A2 (en) * 2006-11-29 2008-10-30 E. I. Du Pont De Nemours And Company Multiaxial polyethylene fabric and laminate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2012100889A1 *

Also Published As

Publication number Publication date
CN103354848A (en) 2013-10-16
KR20140006843A (en) 2014-01-16
DE102011003186A1 (en) 2012-07-26
US20130302695A1 (en) 2013-11-14
WO2012100889A1 (en) 2012-08-02
JP2014505147A (en) 2014-02-27

Similar Documents

Publication Publication Date Title
EP2668328A1 (en) Thin macroporous polymer films
DE10336380B4 (en) Ultrathin, porous and mechanically stable nonwoven fabric and its use
EP2616580B1 (en) Highly functional spunbonded fabric made from particle-containing fibres and method for producing same
DE4303362C2 (en) Separator material for batteries and process for its manufacture
EP0432586B1 (en) Non-woven bi-layer material, specially with long-term filter properties, and process for its manufacture
DE69430377T2 (en) AFTER-TREATMENT OF LAMINATED FLEECE
DE202004021610U1 (en) Soft and three-dimensional nonwoven fabric
DE2731291A1 (en) SUEDE-LIKE RAIL MATERIAL AND METHOD OF ITS MANUFACTURING
EP2547816A1 (en) Stitched multiaxial scrims
DE29617779U1 (en) Water vapor permeable and water-repellent lining material for the clothing and shoe industry
EP1772258B1 (en) Use of a web laminate for production of fibre-reinforced parts and fibre-reinforced part
DE10135111A1 (en) Composite nonwoven fabric with high transverse strength, process for its production and use
WO2017032778A1 (en) Cleaning textile
EP2758580B1 (en) Non-woven material with a matrix containing elementary filaments
DE69331065T2 (en) FOLLOW-UP OF FABRICS.
DE102010047105A1 (en) Multilayer composite material with elastic properties, comprises a foam layer, and one side of the foam layer is covered with a fibrous layer, which is formed from fibers and/or filaments
EP1838523B1 (en) Multilayer fabric
DE10345953B4 (en) Nonwoven fabric and process for its production
DE10141410B4 (en) Battery separators, processes for their preparation and the use thereof
DE102019203986B4 (en) NON-WOVEN ARTICLES
DE102015010105A1 (en) A stretchable nonwoven fabric, process for making a stretchable nonwoven fabric and use thereof
EP4355942A1 (en) Method for manufacturing a polymer nonwoven fabric
DE4425138C2 (en) Sheets made of synthetic polymers and process for their production
WO1992012005A1 (en) Matrix-free composite material
WO2016165835A1 (en) Nonwoven layer for heat protection textiles

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: 20130626

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)
RIC1 Information provided on ipc code assigned before grant

Ipc: D04H 1/54 20120101AFI20140702BHEP

17Q First examination report despatched

Effective date: 20140709

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 2/16 20060101ALI20140904BHEP

Ipc: D04H 1/54 20120101ALI20140904BHEP

Ipc: D04H 3/04 20120101AFI20140904BHEP

Ipc: D04H 1/541 20120101ALI20140904BHEP

Ipc: H01M 10/0525 20100101ALI20140904BHEP

Ipc: D04H 1/555 20120101ALI20140904BHEP

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: 20170701