Classifications

• • 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
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/06—Coating with compositions not containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of 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
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • 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
  • H01M50/406—Moulding; Embossing; Cutting
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
  • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
  • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • 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

Definitions

• the present invention relates to a coated porous film and its
• NiCd nickel-cadmium
• lithium, lithium-ion, lithium-polymer, and alkaline-earth batteries are increasingly being used as accumulators.
• Batteries and accumulators always consist of two electrodes immersed in an electrolyte solution and a separator separating the anode and cathode.
• the different battery types differ by the used
• Electrode material the electrolyte and the separator used.
• Battery separator has the task of cathode and anode in batteries
• the separator must be a barrier which electrically insulates the two electrodes from each other to avoid internal short circuits. At the same time, however, the separator must be permeable to ions so that the electrochemical reactions in the cell can proceed.
• a battery separator must be thin, so that the internal resistance is as low as possible and a high packing density can be achieved. That's the only way to be good
• CONFIRMATION COPY nowadays, mainly fine-pored materials, such as nonwovens and membranes, are in use.
• lithium batteries In lithium batteries, the occurrence of short circuits is a problem. Under thermal stress, the lithium ion batteries may cause the battery separator to melt, resulting in a short circuit with devastating consequences. Similar dangers exist if the lithium batteries are mechanically damaged or overloaded by faulty electronics of the chargers. To increase the safety of lithium-ion batteries have been in the
• polypropylene membranes are advantageous because of the good puncture resistance, but the melting point of the polypropylene is about 164 ° C very close to the flash point of lithium (170 ° C).
• Separator also has a large porosity. Furthermore, they must be lightweight so that a low specific gravity is achieved and they must be absolutely safe. This means that in the event of overheating or mechanical damage, the positive and negative electrodes must be kept separate in order to prevent further chemical reactions that lead to the fire or explosion of the batteries.
• the polyethylene layer melts and occludes the pores of the porous polypropylene layer, thereby interrupting ion flow and thus current flow in the battery.
• the temperature rises further > 160 ° C
• the polypropylene layer and an internal short-circuit will also melt due to contact between the anode and cathode and the resulting
• US201 1 171523 describes a heat-resistant separator obtained by a solvent method.
• inorganic particles chalk, silicates or alumina
• the coating is a continuous, porous, electrically non-conductive ceramic
• a separator is not enough to meet all requirements for a separator for a lithium high energy battery, especially because in this application particular value was placed on the largest possible pores of the separator. With the described there, up to 5 ⁇ large particles, but it is not possible to produce 10 to 40 pm thick separators, since only a few particles would come to lie one above the other. As a result, the separator would inevitably have a high defect and impurity density (eg holes, cracks, etc.).
• WO 2005038946 describes a heat-resistant separator comprising a carrier made of woven or non-woven polymer fibers, with a porous inorganic ceramic layer on and in this carrier which is bonded to the carrier by an adhesive. Again, ensuring a flawless coating as well as the resulting thickness and weight as
• adhesion promoters tend to close the pores and thus drive the resistance unnecessarily high.
• the spalling of the coating during battery manufacture poses an additional safety risk.
• adhesion promoters in the organic electrolytes used in Li batteries need to be insoluble, i.a. do not negatively affect the conductivity of the electrolyte.
• the adhesion to a variety of coatings is given here without the use of a primer.
• Polyolefin separators can today be produced by various processes: filler process; Cold drawing, extraction method and ⁇ -crystallite method. These methods basically differ by the different mechanisms by which the pores are generated. For example, can be produced by the addition of very high amounts of filler porous films. The pores are created by stretching
• the pores are in principle produced by dissolving out a component from the polymer matrix by means of suitable solvents.
• suitable solvents a variety of variants have developed, which differ in the nature of the additives and the appropriate solvents.
• Both organic and inorganic additives can be extracted. This extraction can be done as the last step in the production of the film or combined with a subsequent drawing.
• the disadvantage in this case is the ecologically and economically questionable extraction step.
• ß-crystallites in high concentrations.
• the ⁇ phase is converted into the alpha modification of the polypropylene. Since these different crystal forms differ in density, here too many microscopic defects, which are torn to pores by stretching, are initially produced.
• the films produced by this process have good porosities and good mechanical strength in the longitudinal and transverse directions and a very good economy. These films are also called hereinafter ⁇ -porous films. To improve the porosity, a higher orientation can be introduced in the longitudinal direction before the transverse extension.
• the object of the present invention was therefore to provide on the one hand a porous flexible film which has a high porosity and
• porous flexible film should additionally provide adequate protection against internal short circuits when used as a separator membrane.
• inorganic, preferably ceramic, coated Separatorfolien based on porous polyolefin films are produced when the inorganic, preferably ceramic, coating on a biaxially oriented, single or multilayer porous film whose porosity is produced by conversion of ß-crystalline polypropylene during stretching of the film, which at least comprises a porous layer and this layer contains at least one propylene polymer and ⁇ -nucleating agent, wherein the film before the coating has a Gurley value of ⁇ 1000s, is applied.
• the present invention thus provides a biaxially oriented, single- or multi-layered porous film which comprises at least one porous layer and this layer contains at least one propylene polymer,
• the porosity of the porous film is from 30% to 80% and
• the permeability of the porous film is ⁇ 1000s (Gurley value), characterized in that
• the porous film has an inorganic, preferably ceramic, coating and
• the coated porous film has a Gurley value of ⁇ 1500s.
• the ceramic coated separator films of the invention based on porous polyolefin films comprises a porous, biaxially oriented film
• BOPP Polypropylene
• Porosity of the film according to the invention is preferably produced by converting ⁇ -crystalline polypropylene during stretching of the film, wherein at least one ⁇ -nucleating agent is present in the film.
• Such BOPP films are also particularly suitable for use as a separator in double-layer capacitors (DSC).
• the films used according to the invention for the coating have a longitudinal orientation after a moderate orientation in the longitudinal direction and are then oriented in the transverse direction that they as a BOPP film a high
• the films used according to the invention for the coating can be constructed in one or more layers.
• the production of such single-layered or multi-layered porous polypropylene film in which propylene polymer and ⁇ -nucleating agent is melted in an extruder and extruded through a flat die onto a take-off roll has already been described in detail in DE-A-102010018374.
• the melt film cools on the take-off roll to form ⁇ -crystallites and solidifies. Subsequently, this film is stretched in the longitudinal direction and then directly in the transverse direction.
• the films used according to the invention for coating can also be wound in the longitudinal direction after drawing and at a later time in a second
• Longitudinal stretching process is greater or less than the process speed of the transverse stretching process.
• porous BOPP films used according to the invention for coating comprise at least one porous layer consisting of propylene polymers,
• propylene homopolymers and / or propylene block copolymers constructed and contains ß-nucleating agent.
• other polyolefins may additionally be included in minor amounts, provided they do not adversely affect porosity and other essential properties.
• the microporous layer optionally additionally contains customary additives, for example stabilizers and / or neutralizing agents in respective effective amounts.
• Suitable propylene homopolymers contain from 98 to 100 wt .-%, preferably 99 to 100 wt .-% of propylene units and have a melting point (DSC) of 150 ° C or higher, preferably 155 to 170 ° C, and generally a
• Propylene homopolymers having an n-heptane-soluble fraction of less than 15% by weight, preferably from 1 to 10% by weight, are preferred propylene homopolymers for the layer.
• isotactic propylene homopolymers with a high chain isotacticity of at least 96%, preferably 97% 99% ( 13 C NMR, triad method) can be used.
• HIPP polymers high isotactic polypropylenes
• HCPP high crystalline polypropylenes
• Propylene block copolymers have a melting point of about 140 to 170 ° C, preferably from 145 to 165 ° C, especially 150 to 160 ° C and a
• the comonomer preferably ethylene content is for example between 1 and 20 wt .-%, preferably 1 and 10 wt .-%.
• the melt flow index of the propylene block copolymers is generally in a range of 1 to 20 g / 10 min, preferably 1 to 10 g / 10 min.
• the porous layer may additionally contain other polyolefins, provided that they do not adversely affect the properties, in particular the porosity and the mechanical strengths.
• Other polyolefins include, for example, random copolymers of ethylene and propylene having an ethylene content of 20% by weight or less, random copolymers of propylene with C 4 -C 8 olefins having an olefin content of 20% by weight or less, terpolymers of propylene, Ethylene and butylene with an ethylene content of 10 wt .-% or less and with a butylene content of 15% by weight or less,
• the porous layer is only made of
• Coating used porous BOPP films no polyolefins, which were produced by means of so-called metallocene catalysts.
• ⁇ -nucleating agents for the porous layer.
• Such ⁇ -nucleating agents, as well as their mode of action in a polypropylene matrix, are per se known in the art and will be described in detail below.
• highly active ⁇ -nucleating agents are preferably used which, on cooling a propylene homopolymer melt, produce a ⁇ content of 40-95%, preferably of 50-85% (DSC).
• the ß-portion is cooled from the DSC
• a two-component ⁇ -nucleation system of calcium carbonate and organic is preferred Dicarboxylic acids, which is beschoben in DE 3610644, which is hereby incorporated by reference.
• Particularly advantageous are calcium salts of dicarboxylic acids, such as calcium pimelate or calcium suberate as described in DE 4420989, to which also expressly incorporated by reference.
• the dicarboxamides described in EP-0557721, in particular N, N-dicyclohexyl-2,6-naphthalenedicarboxamides, are also suitable ⁇ -nucleating agents.
• the cooling of the melt film is preferably carried out at a temperature of 60 to 140 ° C, in particular 80 to 130 ° C, for example 85 to 128 ° C. Slow cooling also promotes the growth of ⁇ -crystallites, therefore the take-off speed, i. the
• the take-off speed is preferably less than 25 m / min, in particular 1 to 20 m / min.
• the residence time is generally 20 to 300s; preferably 30 to 200s.
• the porous layer generally contains 45 to ⁇ 100% by weight, preferably 50 to 95% by weight, of propylene homopolymer and / or propylene block copolymer and 0.001 to 5% by weight, preferably 50 to 10,000 ppm of at least one ⁇ -nucleating agent on the weight of the porous layer.
• Propylene homopolymers or the block copolymer reduced accordingly.
• the amount of the additional polymers in the layer will be 0 to ⁇ 10% by weight, preferably 0 to 5% by weight, in particular 0.5 to 2% by weight, if these are additionally present.
• said propylene homopolymer or propylene block copolymer portion is reduced when higher amounts of up to 5 wt .-% nucleating agent are used.
• the layer can contain conventional stabilizers and neutralizing agents, as well optionally further additives, contained in the usual small amounts of less than 2 wt .-%.
• the porous layer is composed of a mixture of propylene homopolymer and propylene block copolymer.
• the porous layer in these embodiments generally contains from 50 to 85% by weight, preferably from 60 to 75% by weight, of propylene homopolymers and from 15 to 50% by weight of propylene block copolymers, preferably from 25 to 40% by weight, and from 0.001 to 5 % By weight, preferably 50 to 0,000 ppm, of at least one ⁇ -nucleating agent, based on the weight of the layer, and, if appropriate, the already mentioned additives, such as stabilizers and neutralizing agents.
• porous film according to the invention contain from 50 to 10,000 ppm, preferably from 50 to 5000 ppm, in particular from 50 to 2000 ppm of calcium pimelate or calcium suberate as ⁇ -nucleating agent in the porous layer.
• the porous film may be one or more layers.
• the thickness of the film is generally in a range of 10 to 100 ⁇ m, preferably 15 to 60 ⁇ m, for example 15 to 40 ⁇ m.
• the porous film may be provided on its surface with a corona, flame or plasma treatment to improve the filling with electrolytes.
• the film comprises further porous layers which are constructed as described above, wherein the
• Composition of different porous layer does not necessarily have to be identical.
• the thickness of the individual layers is generally 2 to 50pm.
• the density of the porous film to be coated is generally in a range of 0.1 to 0.6 g / cm 3 , preferably 0.2 to 0.5 g / cm 3 .
• the bubble point of the film to be coated should not exceed 350nm,
• the mean pore diameter should be in the range from 20 to 350, in particular from 40 to 300, particularly preferably 50 to 300 nm, and the mean pore diameter should be in the
• the porosity of the porous film to be coated is generally in a range of 30% to 80%, preferably 50% to 70%.
• the porous film to be coated in particular the porous BOPP film, has a defined roughness Rz (ISO 4287, roughness measurement one line, amplitude parameter roughness profile, device Leica DCM3D, Gaussian filter, 0.25 mm) of preferably 0.3 ⁇ m to 6 ⁇ m preferably 0.5 to 5 pm, in particular 0.5 to 3.5 pm.
• Rz defined roughness
• the biaxially oriented, single or multilayer porous film according to the invention has an inorganic, preferably ceramic, coating on at least one side of the surface.
• the coating is electrically insulating.
• the inorganic, preferably ceramic, coating according to the invention comprises ceramic particles, which are also understood as meaning inorganic particles.
• the particle size expressed as D50 value is in the range between 0.05 and 15pm, preferably in the range 0, 1 to 10pm. The selection of the exact
• Particle size is dependent on the thickness of the inorganic
• the D50 value should not be greater than 50% of the thickness of the inorganic, preferably ceramic, coating, preferably should not be greater than 33% of the thickness of the inorganic, preferably ceramic, coating, in particular should not be greater than 25% of the thickness of the inorganic, preferably ceramic, coating.
• the D90 value is not greater than 50% of the thickness of the inorganic, preferably ceramic, coating, preferably not greater than 33% of the thickness of the inorganic, preferably ceramic, coating, in particular not greater than 25% of the thickness the inorganic, preferably ceramic, coating.
• inorganic, preferably ceramic, particles in the context of the present invention, all natural or synthetic minerals are understood, provided they have the aforementioned particle sizes.
• the inorganic, preferably ceramic, particles are not limited in terms of particle geometry, but preferred are spherical particles.
• the inorganic, preferably ceramic, particles may be crystalline, partially crystalline (at least 30% crystallinity) or non-crystalline.
• ceramic particles are understood as meaning materials based on silicate raw materials, oxidic raw materials, in particular metal oxides, and / or non-oxidic and non-metallic raw materials.
• Suitable silicate raw materials include materials having a Si04 tetrahedron, for example, layer or framework silicates.
• Suitable oxidic raw materials are, for example, aluminum oxides, zirconium oxides, barium titanate, lead zirconium titanates, ferrites and zinc oxide.
• Suitable non-oxidic and non-metallic raw materials are, for example, silicon carbide, silicon nitride, aluminum nitride, boron nitride, titanium boride and
• the particles used according to the invention consist of electrically insulating materials, preferably a non-electrically conductive oxide of the metals Al, Zr, Si, Sn, Ti and / or Y.
• electrically insulating materials preferably a non-electrically conductive oxide of the metals Al, Zr, Si, Sn, Ti and / or Y.
• the production of such particles is described in detail, for example, in DE-A-10208277.
• the inorganic, preferably ceramic, particles are preferably polycrystalline materials, in particular those whose crystallinity is more than 30%.
• the inorganic, preferably ceramic, coating according to the invention preferably has a thickness of from 0.5 ⁇ m to ⁇ , in particular from 1 m to 40 m.
• the application amount of inorganic, preferably ceramic, coating is preferably 0.5 g / m 2 to 80g / m 2, in particular 1 g / m 2 to 40g / m 2, based on the binder plus particles after drying.
• the amount of inorganic, preferably ceramic, particles applied is preferably 0.4 g / m 2 to 60 g / m 2 , in particular 0.9 g / m 2 to 35 g / m 2 , based on particles after drying.
• the inorganic, preferably ceramic, coating according to the invention comprises inorganic, preferably ceramic, particles which preferably have a density in the range from 1.5 to 5 g / cm 3 , preferably from 2 to 4.5 g / cm 3 .
• the inorganic, preferably ceramic, coating according to the invention comprises inorganic, preferably ceramic, particles which are preferably a Hardness of min. 2 on the Moh's scale.
• the inventive inorganic, preferably ceramic, coating comprises inorganic, preferably ceramic, particles which preferably have a melting temperature of at least 160 ° C., in particular at least 180 ° C., very particularly preferably at least 200 ° C.
• the said particles should not undergo decomposition at the temperatures mentioned.
• the aforementioned information can be determined by known methods, e.g. DSC (differential scanning calorimetry) or TG (thermogravimetry) can be determined.
• the inventive inorganic, preferably ceramic, coating comprises inorganic, preferably ceramic, particles which preferably have a compressive strength of min. 100 kPa, more preferably from min. 150 kPa, in particular of min. 250kPa.
• Compressive strength means that min. 90% of the existing particles were not destroyed by the applied pressure.
• Coatings are preferably those of a thickness of 0.5 ⁇ to ⁇ and
• coatings which have (i) a thickness of ⁇ , ⁇ to ⁇ , (ii) ceramic particles in the range between 0.05 and 15 ⁇ m (d 50 value),
• coatings which have (i) a thickness of ⁇ , ⁇ to 80 ⁇ , (ii) inorganic, preferably ceramic, particles in the range between 0.05 and 15 ⁇ (d50 value), preferably in the range 0, 1 to 10 ⁇ (d50 value ), whose pressure resistance min. 100 kPa, more preferably from min. 150 kPa, in particular min. 250kPa, and the D50 value is not greater than 50% of Thickness of the inorganic, preferably ceramic, coating is, preferably not greater than 33% of the thickness of the inorganic, preferably ceramic, coating, in particular not greater than 25% of the thickness of the inorganic, preferably ceramic, coating.
• the inorganic, preferably ceramic, coating according to the invention comprises, in addition to the stated inorganic, preferably ceramic,
• Particles still at least one end-bonded binder selected from the group of binders based on polyvinylene dichloride (PVDC), polyacrylates, polymethacrylates, polyethyleneimines, polyesters, polyamides, polyimides,
• PVDC polyvinylene dichloride
• polyacrylates polymethacrylates
• polyethyleneimines polyethyleneimines
• polyesters polyamides
• polyimides polyimides
• Polyurethanes polycarbonates, silicate binders, grafted polyolefins, polymers from the class of halogenated polymers, for example PTFE, and mixtures thereof.
• the binders used in the invention should be electrically insulating, i. have no electrical conductivity. Electrically insulating or none
• the amount of final binder binder selected from the group of binders based on polyvinylene dichloride (PVDC), polyacrylates, polymethacrylates, polyethyleneimines, polyesters, polyamides, polyimides, polyurethanes, polycarbonates, silicate binders, grafted polyolefins, polymers from the class of halogenated polymers, for example PTFE and mixtures thereof, is preferably 0.05 g / m 2 to 20g / m 2, in particular 0, 1 g / m 2 to 10g / m 2. [only binder, dried].
• PVDC Polyvinylendichlorid
• the inventive inorganic, preferably ceramic, coating comprises, based on binder and inorganic, preferably ceramic, particles in the dried state, 98 wt .-% to 50 wt .-% of inorganic, preferably ceramic, particles and 2 wt .-% to 50 wt .-% binder selected from the Group of binders based on polyvinylene dichloride (PVDC), polyacrylates,
• PVDC polyvinylene dichloride
• Polymethacrylates polyethylenimines, polyesters, polyamides, polyimides,
• PVDC Polyvinylene dichloride
• Ceramic coating according to the invention still small amounts of additives that are necessary for handling the dispersion.
• the inorganic, preferably ceramic, coating according to the invention is applied to the porous BOPP film by means of known technologies, for example by knife coating or spraying.
• the inorganic, preferably ceramic, coating is applied as a dispersion.
• These dispersions are preferably present as aqueous dispersions and, in addition to the inventive inorganic, preferably ceramic, particles, at least one of said binders, preferably binders based on polyvinylene dichloride (PVDC), water and optionally organic substances which improve the dispersion stability or the wettability increase porous BOPP film.
• the organic substances are volatile organic substances, such as mono- or polyhydric alcohols, especially those whose boiling point does not exceed 140 ° C. Due to availability, isopropanol, propanol and ethanol are particularly preferred.
• the order of the inorganic, preferably ceramic, particles is particularly preferred.
• Preferred dispersions include:
• PVDC Polyvinylene dichloride
• Polyethyleneimines polyesters, polyamides, polyimides, polyurethanes,
• PVDC Polyvinylene dichloride
• (Iii) optionally 1 wt .-% to 30 wt .-%, particularly preferably 0.01 wt .-% to 0.5 wt .-% of organic substances which improve the dispersion stability or increase the wettability to the porous BOPP film, in particular or polyhydric alcohols,
• the present invention furthermore relates to a process for the production of the inorganic, preferably ceramic, coated porous BOPP film according to the invention.
• the porous film is produced by the known flat film extrusion or coextrusion process.
• the procedure is such that the mixture of propylene homopolymer and / or propylene block copolymer and ß-nucleating agent and optionally further polymers of the respective layer is mixed, melted in an extruder and, optionally together and simultaneously, extruded through a flat die onto a take-off roll or is co-extruded, on which the single- or multilayer melt film is formed to form the
• Crystallite solidifies and cools.
• the cooling temperatures and cooling times are selected so that the highest possible proportion of ⁇ -crystalline polypropylene is formed in the prefilm.
• this temperature of the take-off roll or the take-off rolls is 60 to 140 ° C, preferably 80 to 130 ° C.
• the residence time at this temperature may vary and should be at least 20 to 300 seconds, preferably 30 to 100 seconds.
• the prefilm thus obtained generally contains a proportion of ⁇ -crystallites of 40-95%, preferably 50-85%.
• This precursor film with a high proportion of ⁇ -crystalline polypropylene is then biaxially stretched in such a way that, upon drawing, the ⁇ -crystallites are converted into ⁇ -crystalline polypropylene and a network-like porous structure is formed.
• the biaxial stretching (orientation) will generally be performed sequentially, preferably first longitudinally (in the machine direction) and then transversely (perpendicular to the
• Machine direction is stretched.
• the cooled prefilm is first passed over one or more heating rollers, which heat the film to the appropriate temperature. In general, this temperature is less than 140 ° C, preferably 70 to 120 ° C.
• the longitudinal stretching is then generally carried out with the help of two according to the desired stretch ratio different schnei securedder rollers.
• the longitudinal stretch ratio is in a range from 2: 1 to 6: 1, preferably 3: 1 to 5: 1. To avoid too high
• Orientation in the longitudinal direction of the latitudinal recess is kept low in the longitudinal paths, for example, by setting a comparatively narrow
• the length of the stretched gap is generally 3 to 100 mm, preferably 5 to 50 mm.
• fixing elements such as spreaders contribute to a small latitude.
• the jump should be less than 10%, preferably 0.5-8%, in particular 1-5%.
• the film is first cooled again over appropriately tempered rolls. Subsequently, in the so-called
• Transverse stretching ratio in a range of 2: 1 to 9: 1, preferably 3: 1 - 8: 1.
• the transverse stretching takes place with a moderate to slow transverse stretching speed of> 0 to 40% / s, preferably in a range of 0.5 to 30% / s, in particular 1 to 15% / s.
• the last stretch generally the
• Transverse stretching a surface of the film by one of the known methods corona, plasma or flame treated, so that the filling with electrolyte is favored. This is preferably the surface of the film which is not subsequently coated.
• heat-setting in which the film about 5 to 500s, preferably 10 to 300s long at a
• the film is driven converging immediately before or during the heat-setting, wherein the convergence is preferably 5 to 25%, in particular 8 to 20%. Convergence is understood to mean a slight collapse of the
• Heat setting is. The same applies, of course, for the width of the film web.
• the degree of convergence of the transverse stretching frame is specified as the convergence, which is calculated from the maximum width of the transverse stretching frame B max and the final film width B Fo iie according to the following formula:
• the film is wound in the usual way with a take-up device.
• transverse stretching process Process steps up to and including cooling after longitudinal stretching, hereinafter referred to as longitudinal stretching process and in a second process, which comprises all the process steps according to the longitudinal stretching process, hereinafter called transverse stretching process.
• This embodiment of the method according to the invention as a two-stage method makes it possible to select the method speed of the first method, and thus the respective conditions, in particular cooling and withdrawal speeds, as well as the longitudinal stretching conditions independently of the transverse stretching speed. Accordingly, in the second transverse stretching method, the transverse stretching speed can be slowed down as desired, for example by reducing the speed of the process or by extending the stretching frame, without negatively affecting the formation of the ⁇ -crystallites or the longitudinal stretching conditions.
• This process variant is implemented by the
• the longitudinal stretching method or the transverse stretching method or the sequential method is understood in each case as that speed, for example in m / min, with which the film runs in the case of the respective final winding.
• the conditions can be advantageous in the transverse stretching process both a faster and a slower process speed than in the longitudinal stretching process.
• the process conditions in the process according to the invention for producing the porous films differ from the process conditions which are usually observed in the production of a biaxially oriented film. To achieve a high porosity and permeability, both the cooling conditions during solidification to the pre-foil, and the
• the longitudinal stretching must occur at comparatively low temperatures. In the transverse stretching, these impurities are torn to pores, so that the characteristic network structure of these porous films is formed.
• low temperatures, especially in the longitudinal stretching require high stretching forces, which bring a high orientation in the polymer matrix on the one hand and on the other hand increase the risk of demolition.
• the higher the desired porosity the lower the stretching temperatures must be and the higher the stretching factors must be. Therefore, the process becomes more critical the higher the porosity and permeability of the film should be. Therefore, the porosity can not be arbitrarily increased by higher stretching factors or lowering of the stretching temperature.
• the reduced longitudinal stretching temperature leads to a greatly impaired running safety of the film, as well as to an undesirable increase in the tendency to splice. The porosity may therefore be due to lower
• the inorganic, preferably ceramic, coating according to the invention is applied to the porous BOPP film by means of known technologies, for example by knife coating or spraying or printing, in the form of a dispersion, preferably an aqueous dispersion.
• the inorganic, preferably ceramic, coating is applied directly to the above-prepared porous BOPP film, so that no
• Corona, plasma or flame treatment is necessary and the inorganic, preferably ceramic, coating can be applied directly to the porous BOPP film.
• the application amount of dispersion is preferably between 1 g / m 2 and 80 g / m 2 .
• the freshly coated porous BOPP film is dried by means of commercially available dryers, wherein the binder present cures.
• the drying is usually carried out at temperatures between 50 ° C and 140 ° C.
• the drying times are between 30 seconds and 60 minutes.
• a film can be provided which, due to the high permeability for use in
• the film can advantageously be used in other applications in which a very high permeability is required or has an advantageous effect.
• a highly porous separator in batteries especially in lithium batteries with high performance requirements.
• the inventive inorganic, preferably ceramic, coated separator films based on porous polyolefin films comprises a porous, biaxially oriented film of polypropylene with a porosity of 30 to 80% and a permeability of ⁇ 1000s (Gurley value) and the permeability of the
• Separator films according to the invention having an inorganic, preferably ceramic, coating is ⁇ 1500 s (Gurley value).
• the inorganic, preferably ceramic, coating present on the separator film according to the invention exhibits a good adhesion behavior, this being achieved without the use of adhesion promoters.
• the detention behavior is assessed as follows:
• the coating breaks off the edge and can be rubbed off with the fingers.
• a suitable particle size analyzer is
• Microtrac S 3500 for example, a Microtrac S 3500.
• the melt flow index of the propylene polymers was measured according to DIN 53 735 at 2.16 kg load and 230 ° C.
• the melting point in the context of the present invention is the maximum of the DSC curve.
• the determination of the ⁇ -content of the prefilm is likewise carried out via a DSC
• Kri sta 11 in relievesg KU DSC determined as the ratio of the enthalpies of fusion of the ß-crystalline phase (H ß ) to the sum of the enthalpies of ß and ⁇ -crystalline phase (H ß + H).
• the density is determined according to DIN 53 479, method A. Bubble Point:
• the bubble point was measured according to the ASTM F316.
• j e -P Pp ) of the film compared to the density of the pure polypropylene p DD is calculated as follows:
• the permeability of the films was measured with the Gurley Tester 41 10, according to ASTM D 726-58. It determines the time (in seconds) that 100 cm 3 of air will take to permeate through the 1 inch 2 (6,452 cm 2 ) film surface. The pressure difference across the film corresponds to the pressure of a water column of 12.4 cm in height. The time required then corresponds to the Gurley value.
• the jump indicates the change in width of the film during the longitudinal stretching.
• B 0 denotes the width of the film before and Bi corresponding to the width of the film after the Lssensverstreckung.
• the longitudinal direction is the machine direction, as the transverse direction is defined according to the direction transverse to the machine.
• the difference between the determined widths and the original width B 0 times 100 is given as an entry in%.
• Increment B [%] [(B 0 - ⁇ / B 0 ] * 100 [%]
• the inorganic, preferably ceramic, coating three different inorganic coatings were mixed.
• a commercially available PVDC coating DIOFAN® A 297 as a binder with the inorganic particles and by addition of water and isopropanol was adjusted so that the viscosity of the coating allows a uniform spreading by means of wire spinner DIOFAN® A 297 on the polypropylene film.
• the proportion of PVDC's was just chosen so that on the one hand after drying of the solvent component, an abrasion resistant coating is formed and on the other still enough open areas between the ceramic particles is present, so that an open air-permeable, porous structure.
• Coating materials is detailed in Tab 1.
• inorganic particles spherical silicate (Zeeospheres TM, 3M) and TiO2 particles were selected.
• Calcium pimelate as nucleating agent was mixed in the mixer at a concentration of 0.04 wt.% With granules of isotactic polypropylene homopolymer
• the film additionally contained stabilizer and neutralizing agent in conventional amounts.
• the polymer blend was withdrawn after extrusion through a first take-off roll and another roll center, cooled and solidified, then longitudinally stretched, cross-stretched and fixed, specifically the following
• Cooling roller temperature 125 ° C
• the porous film thus prepared was about 20 ⁇ m thick and had a density of 0.30 g / cm 3 and showed a uniform white-opaque appearance.
• the porosity was 66% and the Gurley value was 180 s.
• Calcium pimelate as a nucleating agent was mixed in the mixer at a concentration of 0.04% by weight with granules of isotactic polypropylene homopolymer
• the film additionally contained stabilizer and neutralizing agent in conventional
• the polymer blend was withdrawn after extrusion through a first take-off roll and another roll center, cooled and solidified, then longitudinally stretched, cross-stretched and fixed, specifically the following
• Cooling roller temperature 125 ° C
• the porous film thus prepared was about 20 ⁇ m thick and had a density of 0.30 g / cm 3 and showed a uniform white-opaque appearance.
• the porosity was 68% and the Gurley value 150 s.
• Coating solution 2 differs from Coating 1 by a higher PVDC binder content. After coating, the wetting of the film with the ceramic suspension is uniform. The thus coated film is dried again for one hour at 90 ° C in a drying oven. The coating shows better adhesion after drying than in Example 1 on the film. However, the air permeability (Gurley value) is significantly increased at almost the same application weight of the coating. An increase in the Gurley value from 180 s to 420 s is observed.
• Titanium oxide coating with the composition Coating 3 (Tab.1) applied by hand. After coating, the wetting of the film with the ceramic suspension is uniform. The thus coated film is dried again for one hour at 90 ° C in a drying oven. The coating shows good adhesion to the film after drying. There will be a surge of
• Example 2 It was as in Example 1 microporous BOPP film (Example 2) now with a wire rod (wire diameter: 0.7 mm) silicate coating with the
• Composition Coating 1 (Table 1) applied by hand. The wetting of the film with the ceramic suspension is uniform. After one hour at 90 ° C dried in a drying oven shows the coating despite high coating weight good adhesion to the film. Only a slight increase in the Gurley value from 180 s to 220 s is observed.
• Example 1 On a commercially available microporous separator from Celgard (C200), the silicate coating with the composition Coating 1 (Table 1) was applied by hand as in Example 1 using a wire bar (wire diameter: 0.4 mm). The coating solution shows no wetting and bursts after the
• Wire bar (wire diameter: 0.4mm) tries to apply the silicate coating with the composition Coating 2 (Tab. 1) by hand.
• the coating solution with an increased PVDC content shows no wetting and breaks down again after drying.
• Example 7 (comparison):
• Example 8 (comparison): The Polyolefin Separator Fa. ÜBE was as in Example 2 with a
• Wire bar (wire diameter: 0.4mm) tries to apply the silicate coating with the composition Coating 2 (Tab. 1) by hand. Even the coating with an increased PVDC content shows no wetting and breaks down again after drying.
• Coating 2 with increased PVDC content also shows no wetting and adhesion to the biaxially stretched polypropylene packaging film GND 30 from Treofan.
• Example 4 PDA 20 Coat. 1 0.7 150 200 52 63 yes yes

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