US20100297491A1 - Microporous Polymeric Membrane, Battery Separator, and Battery - Google Patents

Microporous Polymeric Membrane, Battery Separator, and Battery Download PDF

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Publication number
US20100297491A1
US20100297491A1 US12/741,187 US74118708A US2010297491A1 US 20100297491 A1 US20100297491 A1 US 20100297491A1 US 74118708 A US74118708 A US 74118708A US 2010297491 A1 US2010297491 A1 US 2010297491A1
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layer
microporous
membrane
polyethylene
range
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US12/741,187
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Inventor
Takeshi Ishihara
Kohtaro Kimishima
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Toray Battery Separator Film Co Ltd
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Toray Tonen Speciality Separator GK
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Priority to US12/741,187 priority Critical patent/US20100297491A1/en
Assigned to TORAY TONEN SPECIALTY SEPARATOR GODO KAISHA reassignment TORAY TONEN SPECIALTY SEPARATOR GODO KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ISHIHARA, TAKESHI, KIMISHIMA, KOHTARO
Publication of US20100297491A1 publication Critical patent/US20100297491A1/en
Assigned to TORAY TONEN SPECIALTY SEPARATOR GODO KAISHA reassignment TORAY TONEN SPECIALTY SEPARATOR GODO KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TONEN CHEMICAL CORPORATION
Assigned to TORAY BATTERY SEPARATOR FILM GODO KAISHA reassignment TORAY BATTERY SEPARATOR FILM GODO KAISHA CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: TORAY TONEN SPECIALTY SEPARATOR GODO KAISHA
Assigned to TORAY BATTERY SEPARATOR FILM CO., LTD. reassignment TORAY BATTERY SEPARATOR FILM CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: TORAY BATTERY SEPARATOR FILM GODO KAISHA
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • 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
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    • H—ELECTRICITY
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • 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
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/736—Shrinkable
    • 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
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    • B32B2457/10—Batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • 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
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    • Y10T428/249978—Voids specified as micro
    • Y10T428/24998—Composite has more than two layers

Definitions

  • the invention relates to a microporous membrane having suitable permeability, pin puncture strength, shutdown temperature, and rupture temperature.
  • the invention also relates to a battery separator formed by such multi-layer, microporous membrane, and a battery comprising such a separator.
  • Another aspect of the invention relates to a method for making the multi-layer, microporous polyolefin membrane, a method for making a battery using such a membrane as a separator, and a method for using such a battery.
  • Microporous membranes can be used as battery separators in, e.g., primary and secondary lithium batteries, lithium polymer batteries, nickel-hydrogen batteries, nickel-cadmium batteries, nickel-zinc batteries, silver-zinc secondary batteries, etc.
  • the membranes' performance significantly affects the properties, productivity and safety of the batteries. Accordingly, the microporous polyolefin membrane should have suitable mechanical properties, heat resistance, permeability, dimensional stability, shutdown properties, meltdown properties, etc.
  • the batteries it is desirable for the batteries to have a relatively low shutdown temperature and a relatively high meltdown (or rupture) temperature for improved battery-safety properties, particularly for batteries that are exposed to high temperatures during manufacturing, charging, re-charging, use, and/or storage.
  • Improving separator permeability generally leads to an improvement in the battery's storage capacity.
  • High shutdown speed is desired for improved battery safety, particularly when the battery is operated under overcharge conditions.
  • Improving pin puncture strength is desired because roughness of the battery's electrode can puncture the separator during manufacturing leading to a short circuit.
  • Improved thickness uniformity is desired because thickness variations lead to manufacturing difficulties when winding the film on a core.
  • microporous membranes containing polyethylene only i.e., the membrane consists of, or consists essentially of, polyethylene
  • microporous membranes containing polypropylene have low meltdown temperatures
  • microporous membranes containing polypropylene only have high shutdown temperatures.
  • microporous membranes comprising polyethylene and polypropylene as main components have been proposed as improved battery separators. It is therefore desired to provide microporous membranes formed from polyethylene resin and polypropylene resin, and multi-layer, microporous membranes comprising polyethylene and polypropylene.
  • JP7-216118A discloses a battery separator comprising a multi-layer, porous film having two microporous layers. Both layers can contain polyethylene and polypropylene, but in different relative amounts.
  • the percentage of the polyethylene is 0 wt. % to 20 wt. % in the first microporous layer, and 21 wt. % to 60 wt. % in the second microporous layer, based on the combined weight of the polyethylene and polypropylene.
  • the total amount of polyethylene in the film i.e., both microporous layers
  • JP10-195215A discloses a relatively thin battery separator having conventional shutdown and pin-pulling characteristics.
  • the term “pin pulling” refers to the relative ease of pulling a metal pin from a laminate of a separator, a cathode sheet and an anode sheet, which is wound around the pin, to form a toroidal laminate.
  • the multi-layer, porous film contains polyethylene and polypropylene, but in different relative amounts. The percentage of polyethylene is 0 wt. % to 20 wt. % in the inner layer and 61 wt. % to 100 wt. % in the outer layer, based on the total weight of the polyethylene and polypropylene.
  • JP10-279718A discloses a separator designed to prevent unacceptably large temperature increases in a lithium battery when the battery is overcharged.
  • the separator is formed from a multi-layer, porous film made of polyethylene and polypropylene, with different relative amounts of polyethylene and polypropylene in each layer.
  • the film has a polyethylene-poor layer whose polyethylene content is 0 wt. % to 20 wt. %, based on the weight of the polyethylene-poor layer.
  • the second layer is a polyethylene-rich layer which contains 0.5 wt. % or more of polyethylene having a melt index of 3 or more and has a polyethylene content of 61 wt. % to 100 wt. %, based on the weight of the polyethylene-rich layer.
  • the invention relates to a multi-layer microporous membrane, comprising:
  • a first layer material comprising polyethylene and a second layer material comprising polypropylene, the polypropylene having (1) a weight-average molecular weight of 6 ⁇ 10 5 or more, (2) a heat of fusion of 90 J/g or more, and (3) a molecular weight distribution (“MWD” defined as Mw/Mn) in the range of about 2 to about 6, wherein
  • the multi-layer microporous membrane has at least a first microporous layer containing the first layer material, a third microporous layer containing the first layer material, and a second microporous layer containing the second layer material, the second microporous layer being located between the first and third microporous layers, and
  • the total amount of polypropylene in the multi-layer microporous membrane is at least 2.0 wt. % based on the total weight of the microporous membrane.
  • the invention relates to a method for producing a microporous membrane, comprising,
  • the invention relates to a microporous polymeric membrane having a rupture temperature of 180° C. or higher and an air permeability satisfying the relationship A ⁇ 0.097 P-I
  • A is the microporous membrane's Normalized Air Permeability expressed in the units of sec/100 cm 3 /25 ⁇ m
  • P is the microporous membrane's Pin Puncture Strength expressed in the units of mN/25 ⁇ m
  • I is in the range of from 100 to about 250, or about 110 to about 230.
  • I is about 110, in which case the relationship can be expressed as A ⁇ 0.097 P-110.
  • the invention in yet another embodiment, relates to a microporous membrane having Rupture temperature 180° C. or higher and comprising polypropylene wherein the total amount polypropylene in the membrane is ⁇ 2 wt. %, based on the total weight of the membrane.
  • the invention is not limited to microporous membranes.
  • separators comprising such membranes, batteries comprising such separators, and the use of such batteries are all within the scope of the invention.
  • FIG. 1 is a graph showing Air permeability (Y axis) and Pin Puncture Strength (X axis) for various microporous membranes.
  • the membranes described in the Examples are represented by diamonds and the membranes described in the Comparative Examples are represented by triangles.
  • Membranes of the invention but not further exemplified are represented by rectangles.
  • Points represented by circles are membranes which have (i) a Rupture temperature lower (cooler) than 180° C. and/or (ii) an Air Permeability that is greater than 0.097P-I, where I is in the range of about 100 to about 250.
  • I represents the Y intercept of the line plotted on FIG. 1 , which has a slope of about 0.097.
  • Air Permeability is expressed in the units of sec/100 cm 3 /25 ⁇ m and P is the microporous membrane's Pin Puncture Strength expressed in the units of mN/25 ⁇ m (where “/25 ⁇ m” means normalized to the value for a membrane of 25 ⁇ m thickness).
  • FIG. 2 is a graph showing the Rupture temperature of microporous polymeric membranes as a function of the membrane's total polypropylene content, e.g., the total amount as measured by wt. % of first and second polypropylene in the membrane, based on the total weight of the membrane.
  • the membranes described in the Examples are represented by diamonds and the membranes described in the Comparative Examples are represented by triangles. Membranes not further exemplified are represented by asterisks.
  • the multi-layer, microporous membrane comprises three layers, wherein the outer layers (also called the “surface” or “skin” layers) comprise the first microporous layer material and at least one intermediate layer (or “core” layer) comprises the second microporous layer material.
  • the multi-layer, microporous membrane can comprise additional layers, i.e., in addition to the two skin layers and the core layer.
  • the outer layers consist essentially of (or consists of) the first microporous layer material and at least one intermediate layer consists essentially of (or consists of) the second microporous layer material.
  • the core layer can be in planar contact with one or more of the skin layers in a stacked arrangement such as A/B/A with face-to-face stacking of the layers.
  • the membrane can be referred to as a “polyolefin membrane” when the membrane contains polyolefin. While the membrane can contain polyolefin only, this is not required, and it is within the scope of the invention for the membrane to contain polyolefin and materials that are not polyolefin.
  • the multi-layer, microporous polyolefin membrane has at least one layer comprising the first microporous layer material and at least one layer comprising the second microporous layer material.
  • the microporous membrane is a three layer membrane wherein the thickness of the core layer is in the range of about 4.6% to about 50%, or from about 5% to about 30%, or from 5% to about 15% of the total thickness of the multi-layer microporous membrane.
  • the first microporous layer material comprises a first polyethylene and optionally a first polypropylene.
  • the second microporous layer material comprises a second polypropylene and optionally a second polyethylene.
  • the total amount of polyethylene in the multi-layer, microporous polyolefin membrane is in the range of from about 70 wt. % to about 98 wt. %, or from about 90 wt. % to about 97.95 wt. %, or from about 95 wt. % to about 97.9 wt. %, based on the weight of the multi-layer, microporous membrane.
  • the total amount of polypropylene in the multi-layer, microporous membrane is generally greater than 2.0 wt.
  • the wt. % is based on the weight of the membrane's total polyolefin content.
  • the total amount of polypropylene in the multi-layer, microporous membrane can be in the range of from about 2.0 wt. % to about 30 wt. %, e.g., about 2.05 wt. % to about 10 wt. %, or from about 2.1 wt. % to about 5 wt. %, based on the weight of the multi-layer, microporous membrane.
  • the first polyethylene is present in the first microporous layer material in a first polyethylene amount in the range of from about 80 wt. % to about 100 wt. % based on the weight of the first microporous layer material;
  • the first polypropylene is present in the first microporous layer material in a first polypropylene amount in the range of from about 0 wt. % to about 10 wt. % (e.g., from about 0.5 wt. % to about 10 wt. %) based on the weight of the first microporous layer material;
  • the second polyethylene is present in the second microporous layer material in a second polyethylene amount in the range of from about 0 wt.
  • the second polypropylene is present in the second microporous layer material in a second polypropylene amount in the range of from about 1 wt. % to about 100 wt%, e.g., from about 10 wt. % to about 60 wt. %, such as from about 20 wt. % to about 50 wt. % based on the weight of the second microporous layer material.
  • the first polyethylene is a polyethylene having an Mw in the range of about 1 ⁇ 10 4 to about 1 ⁇ 10 7 , or about 1 ⁇ 10 5 to about 5 ⁇ 10 6 , or about 1 ⁇ 10 5 to about 9 ⁇ 10 5 .
  • the first polyethylene can have terminal unsaturation of, e.g., two or more per 10,000 carbon atoms in the polyethylene. Terminal unsaturation can be measured by, e.g., conventional infrared spectroscopic methods.
  • the first polyethylene can be one or more varieties of polyethylene, e.g., PE1, PE2, etc.
  • the first polyethylene comprises PE1.
  • PE1 comprises polyethylene having an Mw ranging from about 4 ⁇ 10 5 to about 8 ⁇ 10 5 .
  • the PE1 can be one or more of an high density polyethylene (“HDPE”), a medium-density polyethylene, a branched low-density polyethylene, or a linear low-density polyethylene.
  • PE1 has an Mn/Mw of ⁇ 100, e.g., in the range of about 3 to about 20.
  • PE1 is at least one of (i) an ethylene homopolymer or (ii) a copolymer of ethylene and a comonomer such as propylene, butene-1, hexene-1, etc, typically in a relatively small amount compared to the amount of ethylene, e.g., 10 mol % or less based on 100% by mol of the copolymer.
  • a copolymer can be produced using a single-site catalyst.
  • the first polyethylene comprises PE2.
  • PE2 comprises polyethylene having an Mw of at least about 1 ⁇ 10 6 .
  • PE2 can be an ultra-high molecular weight polyethylene (“UHMWPE”).
  • UHMWPE ultra-high molecular weight polyethylene
  • PE2 is at least one of (i) an ethylene homopolymer or (ii) a copolymer of ethylene and a comonomer which is typically present in a relatively small amount compared to the amount of ethylene, e.g., 10 mol % or less based on 100% by mol of the copolymer.
  • the comonomer can be, for example, one or more of propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, or styrene.
  • the Mw of PE2 can be in the range, e.g., of from about 1 ⁇ 10 6 to about 15 ⁇ 10 6 , or from about 1 ⁇ 10 6 to about 5 ⁇ 10 6 , or from 1 ⁇ 10 6 to about 3 ⁇ 10 6 .
  • the PE2 has an Mw/Mn in the range of about 4.5 to about 10.
  • the first polyethylene comprises both PE1 and PE2.
  • the amount of PE2 in the first polyethylene can be, e.g., in the range of about 0 wt % to about 50 wt %, or about 1 wt. % to about 50 wt. %, based on the weight of the first polyethylene.
  • the first polyethylene comprises PE1 in an amount ⁇ 92 wt. % and PE2 in an amount ⁇ 8 wt. %, based on the weight of the first polyethylene.
  • the first polyethylene has one or more of the following independently-selected features:
  • the microporous membrane is characterized by one or more of:
  • the second polyethylene can be selected from among the same polyethylenes as the first polyethylene.
  • the second polyethylene comprise PE1, PE2, or both PE1 and PE2.
  • the amount of PE2 in the second polyethylene can be in the range of 0 wt % to about 50 wt. %, or about 1 wt. % to about 50 wt. %, based on the weight of the second polyethylene.
  • the second polyethylene is substantially the same as the first polyethylene.
  • Mw and MWD of the polyethylene and polypropylene are determined using a High Temperature Size Exclusion Chromatograph, or “SEC”, (GPC PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). The measurement is made in accordance with the procedure disclosed in “ Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001)”. Three PLgel Mixed-B columns available from (available from Polymer Laboratories) are used for the Mw and MWD determination.
  • the nominal flow rate is 0.5 cm 3 /min; the nominal injection volume is 300 ⁇ L; and the transfer lines, columns, and the DRI detector are contained in an oven maintained at 145° C.
  • the nominal flow rate is 1.0 cm 3 /min; the nominal injection volume is 300 ⁇ L; and the transfer lines, columns, and the DRI detector are contained in an oven maintained at 160° C.
  • the GPC solvent used is filtered Aldrich reagent grade 1,2,4-Trichlorobenzene (TCB) containing approximately 1000 ppm of butylated hydroxy toluene (BHT).
  • TCB 1,2,4-Trichlorobenzene
  • BHT butylated hydroxy toluene
  • Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of the TCB solvent, and then heating the mixture at 160° C. with continuous agitation for about 2 hours. The concentration of UHMWPE solution was 0.25 to 0.75 mg/ml. Sample solution are filtered off-line before injecting to GPC with 2 ⁇ m filter using a model SP260 Sample Prep Station (available from Polymer Laboratories).
  • the separation efficiency of the column set is calibrated with a calibration curve generated using a seventeen individual polystyrene standards ranging in Mp (“Mp” being defined as the peak in Mw) from about 580 to about 10,000,000.
  • Mp being defined as the peak in Mw
  • the polystyrene standards are obtained from Polymer Laboratories (Amherst, Mass.).
  • a calibration curve (logMp vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard and fitting this data set to a 2nd-order polynomial. Samples are analyzed using IGOR Pro, available from Wave Metrics, Inc.
  • the first layer materials can optionally comprise polypropylene.
  • the polypropylene can be, for example, one or more of (i) a propylene homopolymer or (ii) a copolymer of propylene and a comonomer.
  • the copolymer can be a random or block copolymer.
  • the comonomer can be, e.g., one or more of ⁇ -olefins such as ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, vinyl acetate, methyl methacrylate, and styrene, etc.; and diolefins such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc.
  • the amount of the fifth olefin in the copolymer is preferably in a range that does not adversely affect properties of the multi-layer microporous membrane such as heat resistance, compression resistance, heat shrinkage resistance, etc.
  • the amount of the comonomer is generally >10% by mol based on 100% by mol of the entire copolymer.
  • the polypropylene has one or more of the following properties: (i) the polypropylene has an Mw ranging from about 1 ⁇ 10 4 to about 4 ⁇ 10 6 , or about 3 ⁇ 10 5 to about 3 ⁇ 10 6 ; (ii) the polypropylene has an Mw/Mn ranging from about 1.01 to about 100, or about 1.1 to about 50; (iii) the polypropylene's tacticity is isotactic; (iv) the polypropylene has a heat of fusion of at least about 90 Joules/gram; (v) polypropylene has a melting peak (second melt) of at least about 160° C., (vi) the polypropylene has a Trouton's ratio of at least about 15 when measured at a temperature of about 230° C.
  • the polypropylene has an elongational viscosity of at least about 50,000 Pa sec at a temperature of 230° C. and a strain rate of 25 sec ⁇ 1 .
  • the first polypropylene is substantially the same as the second polypropylene.
  • the second polypropylene has one or more of the following characteristics.
  • the second polypropylene preferably has a weight-average molecular weight of 6 ⁇ 10 5 or more (e.g., in the range of about 9 ⁇ 10 5 to about 2 ⁇ 10 6 ) and a heat of fusion ⁇ Hm (measured by a differential scanning calorimeter (DSC) according to JIS K7122) of 90 J/g or more, and an Mw/Mn ⁇ 100, e.g., in the range of about 2 to about 6.
  • DSC differential scanning calorimeter
  • polypropylene having a weight-average molecular weight of less than 6 ⁇ 10 5 has low dispersibility in the polyethylene resin, its use makes stretching difficult, providing large micro-roughness to a surface of the second porous layer and large thickness variation to the multi-layer, microporous membrane.
  • the polypropylene has a heat of fusion ⁇ Hm of less than 90 J/g, the resultant multi-layer, microporous membrane may have low meltdown properties and permeability.
  • the weight-average molecular weight of the second polypropylene can be, e.g., 8 ⁇ 10 5 or more, or in the range 8 ⁇ 10 5 to 2.0 ⁇ 10 6 .
  • the heat of fusion ⁇ Hm of the polypropylene is 95 J/g or more, or 100 J/g or more, or 110 J/g or more, or 115 J/g or more, e.g., in the range of 100 J/g to 120 J/g.
  • the molecular weight distribution, Mw/Mn is ⁇ 2, e.g., in the range of 2 to 6. In an embodiment, Mw/Mn ⁇ 3, e.g, in the range of 3 to 10.
  • the polypropylene content of the second layer material can be, e.g., in the range of from about 1 wt. % to about 100 wt. %, e.g., from about 20 wt. % to about 80 wt. %, such as from about 20 wt. % to about 50 wt. %, based on the weight of the second layer material.
  • the type of the polypropylene is not particularly critical, but may be a propylene homopolymer, a copolymer of propylene and a comonomer, or a mixture thereof, the homopolymer being preferable.
  • the copolymer may be a random or block copolymer.
  • the comonomer can be, for example, ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene, vinyl acetate, methyl methacrylate, styrene, and combinations thereof
  • the amount of comonomer is, e.g., less than 10 mol % based on 100 mol % of the copolymer.
  • the second polypropylene has one or more of the following properties: (i) the polypropylene has an Mw in the range of from about 1 ⁇ 10 4 to about 4 ⁇ 10 6 , or about 6 ⁇ 10 5 to about 3 ⁇ 10 6 ; (ii) the polypropylene has an Mw/Mn in the range of from about 1.01 to about 100, or about 2 to about 6; (iii) the polypropylene's tacticity is isotactic; (iv) the polypropylene has a heat of fusion of at least about 95 Joules/gram; (v) the polypropylene has a melting peak “Tm” (second melt) of at least about 160° C., (vi) the polypropylene has a Trouton's ratio of at least about 15 when measured at a temperature of about 230° C.
  • the polypropylene has an elongational viscosity of at least about 50,000 Pa sec at a temperature of 230° C. and a strain rate of 25 sec ⁇ 1 .
  • the polypropylene has a crystallinity ⁇ 50%, e.g., in the range of 55% to about 75%, such as in the range of 65% to 70%.
  • ⁇ Hm, Mw, and Mn of polypropylene are determined by the methods disclosed in PCT Patent Publication No. WO2007/132942, which is incorporated by reference herein in its entirety.
  • the first microporous layer material is made by combining a first polyolefin composition and a first diluent to form, e.g., a first polyolefin solution. Since the diluent produces a multi-layer microporous membrane, the diluent can also be called a process solvent or a membrane-forming solvent.
  • a first polyolefin composition e.g., a first polyolefin solution.
  • the diluent can also be called a process solvent or a membrane-forming solvent.
  • the first polyethylene resin comprises the first polyethylene, where the first polyethylene is as described above in section [1].
  • the first polyethylene resin can be a mixture of a polyethylene resin having a lower Mw than UHMWPE (such as HDPE) and UHMWPE resin.
  • Multi-stage polymerization can be used to obtain the desired Mw/Mn ratio in the first polyethylene resin.
  • a two-stage polymerization method can be used, forming a relatively high-molecular-weight polymer component in the first stage, and forming a relatively low-molecular-weight polymer component in the second stage. While not required, this method can be used, for example, when the first polyethylene resin comprises PE1.
  • the desired Mw/Mn ratio of the polyethylene resin can be selected by adjusting the relative molecular weights and relative amounts of the first and second polyethylene.
  • the first polyolefin composition can optionally further comprise a first polypropylene resin.
  • the first polypropylene resin comprises the first polypropylene, where the first polypropylene is as described above in section [1].
  • the amount of process solvent in the first polyolefin solution can be in the range. e.g., of from about 25 wt. % to about 99 wt. % based on the weight of the first polyolefin solution.
  • the amount of the first polyethylene resin in the first polyolefin composition can be in the range. e.g., of from about 50 wt. % to about 99 wt. % based on the weight of the first polyolefin composition.
  • the balance of the first polyolefin composition can be the first polypropylene.
  • the second microporous layer material is made from a second polyolefin solution that is generally selected independently of the first polyolefin solution.
  • the second polyolefin solution comprises a second polyolefin composition and a second diluent which can be the same as the first diluent.
  • the second diluent can be referred to as a second membrane-forming solvent or a process solvent.
  • the second polyolefin composition comprises a second polyethylene resin and a second polypropylene resin.
  • the second polyethylene resin comprises the second polyethylene as described above in section [1].
  • the second polypropylene resin comprises the second polypropylene as described above in section [1].
  • the amount of process solvent in the second polyolefin solution can be in the range. e.g., of from about 25 wt. % to about 99 wt. % based on the weight of the second polyolefin solution.
  • the amount of the second polyethylene resin in the second polyolefin composition can be in the range. e.g., of from about 5 wt. % to about 95 wt. % based on the weight of the second polyolefin composition.
  • the balance of the second polyolefin composition can be the second polypropylene.
  • each of the first and second polyolefin compositions can further comprise a third polyolefin selected from the group consisting of polybutene-1, polypentene-1, poly-4-methylpentene-1, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene and an ethylene ⁇ -olefin copolymer (except for an ethylene-propylene copolymer).
  • the third polyolefin can, for example, have an Mw in the range of about 1 ⁇ 10 4 to about 4 ⁇ 10 6 .
  • the first and/or second polyolefin composition can further comprise a polyethylene wax, e.g., one having an Mw in the range of about 1 ⁇ 10 3 to about 1 ⁇ 10 4 .
  • these species should be present in amounts less than an amount that would cause deterioration in the desired properties (e.g., meltdown, shutdown, etc.) of the multi-layer, microporous membrane.
  • the third polyolefin is one or more of polybutene-1, polypentene-1, poly-4-methylpentene-1, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, and polystyrene
  • the third polyolefin need not be a homopolymer, but may be a copolymer containing other ⁇ -olefins.
  • the multi-layer microporous membrane generally comprises the polyolefin used to form the polyolefin solution.
  • a small amount of washing solvent and/or process solvent can also be present, generally in amounts less than 1 wt % based on the weight of the microporous polyolefin membrane.
  • a small amount of polyolefin molecular weight degradation might occur during processing, but this is acceptable.
  • molecular weight degradation during processing if any, causes the value of Mw/Mn of the polyolefin in the membrane to differ from the Mw/Mn of the first or second polyolefin solution by no more than about 50%, or no more than about 1%, or no more than about 0.1%.
  • the microporous polyolefin membrane is a two-layer membrane. In another embodiment, the microporous polyolefin membrane has at least three layers.
  • the production of the microporous polyolefin membrane will be mainly described in terms of two-layer and three-layer membranes, although those skilled in the art will recognize that the same techniques can be applied to the production of membranes or membranes having at least four layers.
  • the three-layer microporous polyolefin membrane comprises first and third microporous layers constituting the outer layers of the microporous polyolefin membrane and a second layer situated between (and optionally in face-to-face contact with) the first and third layers.
  • the first and third layers are produced from a first mixture of polymer and diluent, e.g., a first polyolefin solution and the second (or inner) layer is produced from the second mixture of polymer and diluent, e.g., a second polyolefin solution.
  • the first and third layers are produced from the second polyolefin solution and the second layer is produced from the first polyolefin solution. While the invention is described in terms of extruding polyolefin solutions, it is not limited thereto, and any extrudable mixture of polymer and diluent can be used.
  • the first method for producing a multi-layer membrane comprises the steps of (1) combining (e.g., by melt-blending) a first polyolefin composition and a first diluent to prepare a first polyolefin solution, (2) combining a second polyolefin composition and a second diluent to prepare a second polyolefin solution, (3) extruding (preferably simultaneously) the first and second polyolefin solutions through at least one die to form an extrudate, (4) cooling the extrudate to form a cooled extrudate, e.g., a multi-layer, gel-like sheet, (5) removing the membrane-forming solvent from the multi-layer, sheet to form a solvent-removed sheet, and (6) drying the solvent-removed gel-like sheet to remove volatile species, if any, in order to form the multi-layer, microporous polyolefin membrane.
  • An optional stretching step (7), and an optional hot solvent treatment step (8), etc. can be conducted between steps (4) and (5), if desired.
  • an optional step (9) of stretching a multi-layer, microporous membrane, an optional heat treatment step (10), an optional cross-linking step with ionizing radiation (11), and an optional hydrophilic treatment step (12), etc. can be conducted if desired.
  • the order of the optional steps is not critical.
  • the first polyolefin composition comprises polyolefin resins as described above that can be combined, e.g., by dry mixing or melt blending with an appropriate membrane-forming solvent to produce the first polyolefin solution.
  • the first polyolefin solution can contain various additives such as one or more antioxidant, fine silicate powder (pore-forming material), etc., provided these are used in a concentration range that does not significantly degrade the desired properties of the multi-layer, microporous polyolefin membrane.
  • the first process solvent is optionally a solvent that is liquid at room temperature. While not wishing to be bound by any theory or model, it is believed that the use of a liquid solvent to form the first polyolefin solution makes it possible to conduct stretching of the gel-like sheet at a relatively high stretching magnification.
  • the first membrane-forming solvent can be at least one of aliphatic, alicyclic or aromatic hydrocarbons such as nonane, decane, decalin, p-xylene, undecane, dodecane, liquid paraffin, etc.; mineral oil distillates having boiling points comparable to those of the above hydrocarbons; and phthalates liquid at room temperature such as dibutyl phthalate, dioctyl phthalate, etc.
  • non-volatile liquid solvents such as liquid paraffin can be used, either alone or in combination with other solvents.
  • a solvent which is miscible with polyethylene in a melt blended state but solid at room temperature can be used, either alone or in combination with a liquid solvent.
  • Such solid solvent can include, e.g., stearyl alcohol, ceryl alcohol, paraffin waxes, etc.
  • the viscosity of the liquid solvent is not a critical parameter.
  • the viscosity of the liquid solvent can range from about 30 cSt to about 500 cSt, or from about 30 cSt to about 200 cSt, at 25° C.
  • it is not a critical parameter when the viscosity at 25° C. is less than about 30 cSt, it can be more difficult to prevent foaming the polyolefin solution, which can lead to difficulty in blending.
  • the viscosity is greater than about 500 cSt, it can be more difficult to remove the liquid solvent from the multi-layer microporous polyolefin membrane.
  • the resins, etc., used to produce to the first polyolefin composition are dry mixed or melt-blended in, e.g., a double screw extruder or mixer.
  • a conventional extruder or mixer or mixer-extruder
  • a double-screw extruder can be used to combine the resins, etc., to form the first polyolefin composition.
  • the membrane-forming solvent can be added to the polyolefin composition (or alternatively to the resins used to produce the polyolefin composition) at any convenient point in the process.
  • the solvent can be added to the polyolefin composition (or its components) at any of (i) before starting melt-blending, (ii) during melt blending of the first polyolefin composition, or (iii) after melt-blending, e.g., by supplying the first membrane-forming solvent to the melt-blended or partially melt-blended polyolefin composition in a second extruder or extruder zone located downstream of the extruder zone used to melt-blend the polyolefin composition.
  • the melt-blending temperature is not critical.
  • the melt-blending temperature of the first polyolefin solution can range from about 10° C. higher than the melting point Tm 1 of the first polyethylene resin to about 120° C. higher than Tm 1 .
  • such a range can be represented as Tm 1 +10° C. to Tm 1 +120° C.
  • the melt-blending temperature can be in the range of from about 140° C. to about 250° C., or from about 170° C. to about 240° C.
  • the screw parameters are not critical.
  • the screw can be characterized by a ratio L/D of the screw length L to the screw diameter D in the double-screw extruder, which can range, for example, from about 20 to about 100, or from about 35 to about 70.
  • L/D the screw length L to the screw diameter D in the double-screw extruder
  • melt-blending can be more difficult
  • L/D is more than about 100
  • faster extruder speeds might be needed to prevent excessive residence time of the polyolefin solution in the double-screw extruder (which can lead to undesirable molecular weight degradation).
  • the cylinder (or bore) of the double-screw extruder can have an inner diameter of in the range of about 40 mm to about 100 mm, for example.
  • the amount of the first polyolefin composition in the first polyolefin solution is not critical. In an embodiment, the amount of first polyolefin composition in the first polyolefin solution can range from about 1 wt. % to about 75 wt. %, based on the weight of the polyolefin solution, for example from about 20 wt. % to about 70 wt. %. Although the amount of first polyolefin composition in the first polyolefin solution is not critical, when the amount is less than about 1 wt. %, it can be more difficult to produce the multi-layer microporous polyolefin membrane at an acceptably efficient rate. Moreover, when the amount is less than 1 wt.
  • the amount of first polyolefin composition solution is greater than about 75 wt. %, it can be more difficult to form the multi-layer, gel-like sheet.
  • the amount of polymer (e.g., the first polyethylene resin) in the first polyolefin solution is preferably in the range of 1 wt. % to 50 wt. %, e.g., 20 wt. % to 40 wt. %, based on the weight of the first polyolefin solution.
  • the amount of polymer is less than 1 wt. %, swelling or neck-in may occur at the die exit during the extrusion of the first polyolefin solution to form a gel-like molding, resulting in decrease in the formability and self-support of the gel-like molding.
  • the amount of polymer is more than 50 wt. %, the formability of the gel-like molding is more difficult.
  • the second polyolefin solution can be prepared by the same methods used to prepare the first polyolefin solution.
  • the second polyolefin solution can be prepared by melt-blending a second polyolefin composition with a second membrane-forming solvent.
  • the second membrane-forming solvent can be selected from among the same solvents as the first membrane-forming solvent.
  • the second membrane-forming solvent can be (and generally is) selected independently of the first membrane-forming solvent, the second membrane-forming solvent can be the same as the first membrane-forming solvent, and can be used in the same relative concentration as the first membrane-forming solvent is used in the first polyolefin solution.
  • the second polyolefin composition is generally selected independently of the first polyolefin composition.
  • the second polyolefin composition comprises the second polyethylene resin and the second polypropylene resin.
  • the method for preparing the second polyolefin solution differs from the method for preparing the first polyolefin solution, only in that the mixing temperature is preferably in a range from the melting point (Tm2) of the second polypropylene to Tm2+90° C.
  • the first polyethylene resin is present in the first polyolefin solution in an amount in the range of from about 0.5 wt. % to about 75 wt. % based on the total weight of polyolefin in the first polyolefin solution
  • the first polyolefin solution optionally comprises a first polypropylene resin, the polypropylene resin being present in the first polyolefin solution in an amount in the range of from about 0 wt. % to about 10 wt. % based on the total weight of polyolefin in the first polyolefin solution.
  • the second polypropylene resin is present in the second polyolefin solution in an amount in the range of from about 10 wt. % to about 60 wt. % based on the total weight of polyolefin in the second polyolefin solution
  • the second polyolefin solution optionally comprises a second polyethylene resin, the second polyethylene resin being present in the second polyolefin solution in an amount in the range of from about 40 wt. % to about 90 wt. % based on the total weight of polyolefin in the second polyolefin solution.
  • the first polyolefin solution is conducted from a first extruder to a first die and the second polyolefin solution is conducted from a second extruder to a second die.
  • a layered extrudate in sheet form i.e., a body significantly larger in the planar directions than in the thickness direction
  • the first and second polyolefin solutions are co-extruded from the first and second die with a planar surface of a first extrudate layer formed from the first polyolefin solution in contact with a planar surface of a second extrudate layer formed from the second polyolefin solution.
  • a planar surface of the extrudate can be defined by a first vector in the machine direction of the extrudate and a second vector in the transverse direction of the extrudate.
  • a die assembly is used where the die assembly comprises the first and second die, as for example when the first die and the second die share a common partition between a region in the die assembly containing the first polyolefin solution and a second region in the die assembly containing the second polyolefin solution.
  • a plurality of dies is used, with each die connected to an extruder for conducting either the first or second polyolefin solution to the die.
  • the first extruder containing the first polyolefin solution is connected to a first die and a third die, and a second extruder containing the second polyolefin solution is connected to a second die.
  • the resulting layered extrudate can be co-extruded from the first, second, and third die (e.g., simultaneously) to form a three-layer extrudate comprising a first and a third layer constituting surface layers (e.g., top and bottom layers) produced from the first polyolefin solution; and a second layer constituting a middle or intermediate layer of the extrudate situated between and in planar contact with both surface layers, where the second layer is produced from the second polyolefin solution.
  • a three-layer extrudate comprising a first and a third layer constituting surface layers (e.g., top and bottom layers) produced from the first polyolefin solution; and a second layer constituting a middle or intermediate layer of the extrudate situated between and in planar contact with both surface layers, where the second layer is produced from the second polyolefin solution.
  • the same die assembly is used but with the polyolefin solutions reversed, i.e., the second extruder containing the second polyolefin solution is connected to the first die and the third die, and the first extruder containing the first polyolefin solution is connected to the second die.
  • die extrusion can be conducted using conventional die extrusion equipment.
  • extrusion can be conducted by a flat die or an inflation die.
  • multi-manifold extrusion can be used, in which the first and second polyolefin solutions are conducted to separate manifolds in a multi-layer extrusion die and laminated at a die lip inlet.
  • block extrusion can be used, in which the first and second polyolefin solutions are first combined into a laminar flow (i.e., in advance), with the laminar flow then connected to a die.
  • Die selection is not critical, and, e.g., a conventional multi-layer-sheet-forming, flat or inflation die can be used.
  • Die gap is not critical.
  • the multi-layer-sheet-forming flat die can have a die gap of about 0.1 mm to about 5 mm.
  • Die temperature and extruding speed are also non-critical parameters.
  • the die can be heated to a die temperature ranging from about 140° C. to about 250° C. during extrusion.
  • the extruding speed can range, for example, from about 0.2 m/minute to about 15 m/minute.
  • the thickness of the layers of the layered extrudate can be independently selected.
  • the gel-like sheet can have relatively thick surface layers (or “skin” layers) compared to the thickness of an intermediate layer of the layered extrudate.
  • each surface or intermediate layer can be produced using either the first polyolefin solution and/or the second polyolefin solution.
  • the multi-layer extrudate can be formed into a multi-layer, gel-like sheet by cooling, for example. Cooling rate and cooling temperature are not particularly critical.
  • the multi-layer, gel-like sheet can be cooled at a cooling rate of at least about 50° C./minute until the temperature of the multi-layer, gel-like sheet (the cooling temperature) is approximately equal to the multi-layer, gel-like sheet's gelation temperature (or lower).
  • the extrudate is cooled by exposing the extrudate to a temperature of about 25° C. or lower in order to form the multi-layer gel-like sheet.
  • cooling the layered extrudate sets the polyolefin micro-phases of the first and second polyolefin solutions for separation by the membrane-forming solvent or solvents. It has been observed that in general a slower cooling rate (e.g., less than 50° C./minute) provides the multi-layer, gel-like sheet with larger pseudo-cell units, resulting in a coarser higher-order structure. On the other hand, a relatively faster cooling rate (e.g., 80° C./minute) results in denser cell units.
  • the cooling rate of the extrudate is less than 50° C./minute, increased polyolefin crystallinity in the layer can result, which can make it more difficult to process the multi-layer, gel-like sheet in subsequent stretching steps.
  • the choice of cooling method is not critical.
  • conventional sheet cooling methods can be used.
  • the cooling method comprises contacting the layered extrudate with a cooling medium such as cooling air, cooling water, etc.
  • the extrudate can be cooled via contact with rollers cooled by a cooling medium, etc.
  • At least a portion of the first and second membrane-forming solvents are removed (or displaced) from the multi-layer gel-like sheet in order to form a solvent-removed gel-like sheet.
  • a displacing (or “washing”) solvent can be used to remove (wash away, or displace) the first and second membrane-forming solvents.
  • the removal of the membrane-forming solvent provides a porous membrane constituted by fibrils forming a fine three-dimensional network structure and having pores communicating three-dimensionally and irregularly.
  • the choice of washing solvent is not critical provided it is capable of dissolving or displacing at least a portion of the first and/or second membrane-forming solvent.
  • Suitable washing solvents include, for instance, one or more of volatile solvents such as saturated hydrocarbons such as pentane, hexane, heptane, etc.; chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, etc.; ethers such as diethyl ether, dioxane, etc.; ketones such as methyl ethyl ketone, etc.; linear fluorocarbons such as trifluoroethane, C 6 F 14 , C 7 F 16 , etc.; cyclic hydrofluorocarbons such as C 5 H 3 F 7 , etc.; hydrofluoroethers such as C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , etc.; and perfluoroethers such as C 4 F 9 OCF 3 , C 4 F 9 OC 2 F 5 , etc.
  • volatile solvents such as saturated hydrocarbons such as pentane, hexane, heptane
  • the method for removing the membrane-forming solvent is not critical, and any method capable of removing a significant amount of solvent can be used, including conventional solvent-removal methods.
  • the multi-layer, gel-like sheet can be washed by immersing the sheet in the washing solvent and/or showering the sheet with the washing solvent.
  • the amount of washing solvent used is not critical, and will generally depend on the method selected for removal of the membrane-forming solvent.
  • the amount of washing solvent used can range from about 300 to about 30,000 parts by mass, based on the mass of the gel-like sheet. While the amount of membrane-forming solvent removed is not particularly critical, generally a higher quality (more porous) membrane will result when at least a major amount of first and second membrane-forming solvent is removed from the gel-like sheet.
  • the membrane-forming solvent is removed from the gel-like sheet (e.g., by washing) until the amount of the remaining membrane-forming solvent in the multi-layer gel-like sheet becomes less than 1 wt. %, based on the weight of the gel-like sheet.
  • the solvent-removed multi-layer, gel-like sheet obtained by removing at least a portion of the membrane-forming solvent is dried in order to remove the washing solvent.
  • Any method capable of removing the washing solvent can be used, including conventional methods such as heat-drying, wind-drying (moving air), etc.
  • the temperature to which the gel-like sheet is exposed during drying i.e., drying temperature
  • the drying temperature can be equal to or lower than the crystal dispersion temperature Tcd.
  • Tcd is the lower of the crystal dispersion temperature Tcd 1 of the first polyethylene resin and the crystal dispersion temperature Tcd 2 of the second polyethylene resin (when used).
  • the drying temperature can be at least 5° C.
  • the crystal dispersion temperature of the first and second polyethylene resin can be determined by measuring the temperature characteristics of the kinetic viscoelasticity of the polyethylene resin according to ASTM D 4065. In an embodiment, at least one of the first or second polyethylene resins have a crystal dispersion temperature in the range of about 90° C. to about 100° C.
  • drying can be conducted until the amount of remaining washing solvent is about 5 wt. % or less on a dry basis, i.e., based on the weight of the dry multi-layer, microporous polyolefin membrane. In another embodiment, drying is conducted until the amount of remaining washing solvent is about 3 wt. % or less on a dry basis. Insufficient drying can be recognized because it generally leads to an undesirable decrease in the porosity of the multi-layer, microporous membrane. If this is observed, an increased drying temperature and/or drying time should be used. Removal of the washing solvent, e.g., by drying or otherwise, results in the formation of the multi-layer, microporous polyolefin membrane.
  • the multi-layer, gel-like sheet Prior to the step for removing the membrane-forming solvents (namely prior to step 5), the multi-layer, gel-like sheet can be stretched in order to obtain a stretched, multi-layer, gel-like sheet. It is believed that the presence of the first and second membrane-forming solvents in the multi-layer, gel-like sheet results in a relatively uniform stretching magnification. Heating the multi-layer, gel-like sheet, especially at the start of stretching or in a relatively early stage of stretching (e.g., before 50% of the stretching has been completed) is also believed to aid the uniformity of stretching.
  • any method capable of stretching the multi-layer, gel-like sheet to a predetermined magnification can be used.
  • the stretching can be accomplished by one or more of tenter-stretching, roller-stretching, or inflation stretching (e.g., with air).
  • the stretching can be conducted monoaxially (i.e., in either the machine or transverse direction) or biaxially (both the machine or transverse direction). In an embodiment, biaxial stretching is used.
  • the stretching can be simultaneous biaxial stretching, sequential stretching along one planar axis and then the other (e.g., first in the transverse direction and then in the machine direction), or multi-stage stretching (for instance, a combination of the simultaneous biaxial stretching and the sequential stretching).
  • simultaneous biaxial stretching is used.
  • the stretching magnification is not critical.
  • the linear stretching magnification can be, e.g., about 2 fold or more, or about 3 to about 30 fold.
  • the linear stretching magnification can be, e.g., about 3 fold or more in any planar direction.
  • the area magnification resulting from stretching is at least about 9 fold, or at least about 16 fold, or at least about 25 fold.
  • the stretching results in an area magnification of at least about 9 fold the multi-layer microporous polyolefin membrane has a relatively higher pin puncture strength. When attempting an area magnification of more than about 400 fold, it can be more difficult to operate the stretching apparatus.
  • the temperature to which the multi-layer, gel-like sheet is exposed during stretching is not critical.
  • the temperature of the gel-like sheet during stretching can be about (Tm+10° C.) or lower, or optionally in a range that is higher than Tcd but lower than Tm, wherein Tm is the lesser of the melting point Tm 1 of the first polyethylene and the melting point Tm 2 of the second polyethylene (when used).
  • Tm is the lesser of the melting point Tm 1 of the first polyethylene and the melting point Tm 2 of the second polyethylene (when used).
  • this parameter is not critical, when the stretching temperature is higher than approximately the melting point Tm+10° C., at least one of the first or second polyethylene can be in the molten state, which can make it more difficult to orient the molecular chains of the polyolefin in the multi-layer gel-like sheet during stretching.
  • the stretching temperature when the stretching temperature is lower than approximately Tcd, at least one of the first or second polyethylene can be so insufficiently softened that it is difficult to stretch the multi-layer, gel-like sheet without breakage or tears, which can result in a failure to achieve the desired stretching magnification.
  • the stretching temperature ranges from about 90° C. to about 140° C., or from about 100° C. to about 130° C.
  • stretching can be conducted in the presence of a temperature gradient in a thickness direction (i.e., a direction approximately perpendicular to the planar surface of the multi-layer, microporous polyolefin membrane).
  • a thickness direction i.e., a direction approximately perpendicular to the planar surface of the multi-layer, microporous polyolefin membrane.
  • it can be easier to produce a multi-layer, microporous polyolefin membrane with improved mechanical strength.
  • the details of this method are described in Japanese Patent 3347854.
  • the multi-layer, gel-like sheet can be treated with a hot solvent between steps (4) and (5).
  • the hot solvent treatment provides the fibrils (such as those formed by stretching the multi-layer gel-like sheet) with a relatively thick leaf-vein-like structure.
  • leaf-vein-like means that the fibrils have thick trunks and thin fibers extending therefrom in a network structure. The details of this method are described in WO 2000/20493.
  • the dried multi-layer, microporous membrane of step (6) can be stretched, at least monoaxially.
  • the stretching method selected is not critical, and conventional stretching methods can be used such as by a tenter method, etc. While it is not critical, the membrane can be heated during stretching. While the choice is not critical, the stretching can be monoaxial or biaxial. When biaxial stretching is used, the stretching can be conducted simultaneously in both axial directions, or, alternatively, the multi-layer, microporous polyolefin membrane can be stretched sequentially, e.g., first in the machine direction and then in the transverse direction. In an embodiment, simultaneous biaxial stretching is used.
  • step (9) When the multi-layer gel-like sheet has been stretched as described in step (7) the stretching of the dry multi-layer, microporous polyolefin membrane in step (9) can be called dry-stretching, re-stretching, or dry-orientation.
  • the temperature to which the dry multi-layer, microporous membrane is exposed during stretching is not critical.
  • the dry stretching temperature is approximately equal to the melting point Tm or lower, for example in the range of from about the crystal dispersion temperature Tcd to the about the melting point Tm.
  • Tm melting point
  • the dry stretching temperature ranges from about 90° C. to about 135° C., or from about 95° C. to about 130° C.
  • the stretching magnification is not critical.
  • the stretching magnification of the multi-layer, microporous membrane can range from about 1.1 fold to about 1.8 fold in at least one planar (e.g., lateral) direction.
  • the stretching magnification can range from about 1.1 fold to about 1.8 fold in the longitudinal direction (i.e., the “machine direction”) or the transverse direction, depending on whether the membrane is stretched longitudinally or transversely.
  • Monoaxial stretching can also be accomplished along a planar axis between the longitudinal and transverse directions.
  • biaxial stretching is used (i.e., stretching along two planar axis) with a stretching magnification of about 1.1 fold to about 1.8 fold along both stretching axes, e.g., along both the longitudinal and transverse directions.
  • the stretching magnification in the longitudinal direction need not be the same as the stretching magnification in the transverse direction.
  • the stretching magnifications can be selected independently.
  • the dry-stretching magnification is the same in both stretching directions.
  • the membrane can be stretched to a magnification that is larger than 1.8 fold, particularly when during subsequent processing (e.g., heat treatment) the membrane relaxes (or shrinks) in the direction(s) of stretching to a achieve a final magnification of about 1.1 to about 1.8 fold compared to the size of the film at the start of the dry orientation step.
  • the dried multi-layer, microporous membrane can be heat-treated following step (6). It is believed that heat-treating stabilizes the polyolefin crystals in the dried multi-layer, microporous polyolefin membrane to form uniform lamellas.
  • the heat treatment comprises heat-setting and/or annealing. When heat-setting is used, it can be conducted using conventional methods such as tenter methods and/or roller methods. Although it is not critical, the temperature to which the dried multi-layer, microporous polyolefin membrane is exposed during heat-setting (i.e., the “heat-setting temperature”) can range from the Tcd to about the Tm.
  • the heat-setting temperature ranges from about the dry stretching temperature of the multi-layer, microporous polyolefin membrane ⁇ 5° C., or about the dry stretching temperature of the multi-layer, microporous polyolefin membrane ⁇ 3° C.
  • Annealing differs from heat-setting in that it is a heat treatment with no load applied to the multi-layer, microporous polyolefin membrane.
  • the choice of annealing method is not critical, and it can be conducted, for example, by using a heating chamber with a belt conveyer or an air-floating-type heating chamber. Alternatively, the annealing can be conducted after the heat-setting with the tenter clips slackened.
  • the temperature of the multi-layer, microporous polyolefin membrane during annealing i.e., the annealing temperature
  • the annealing temperature ranges from about the melting point Tm or lower, or in a range from about 60° C. to (Tm-10° C.). It is believed that annealing makes it less difficult to produce a multi-layer, microporous polyolefin membrane having relatively high permeability and strength.
  • the multi-layer, microporous polyolefin membrane can be cross-linked (e.g., by ionizing radiation rays such as ⁇ -rays, ⁇ -rays, ⁇ -rays, electron beams, etc.) after step (6).
  • the amount of electron beam radiation can be about 0.1 Mrad to about 100 Mrad, using an accelerating voltage in the range of about 100 kV to about 300 kV. It is believed that the cross-linking treatment makes it less difficult to produce a multi-layer, microporous polyolefin membrane with relatively high meltdown temperature.
  • the multi-layer, microporous polyolefin membrane can be subjected to a hydrophilic treatment (i.e., a treatment which makes the multi-layer, microporous polyolefin membrane more hydrophilic).
  • a hydrophilic treatment i.e., a treatment which makes the multi-layer, microporous polyolefin membrane more hydrophilic.
  • the hydrophilic treatment can be, for example, a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc.
  • the monomer-grafting treatment is used after the cross-linking treatment.
  • any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used, for example, either alone or in combination.
  • a nonionic surfactant is used.
  • the choice of surfactant is not critical.
  • the multi-layer, microporous polyolefin membrane can be dipped in a solution of the surfactant and water or a lower alcohol such as methanol, ethanol, isopropyl alcohol, etc., or coated with the solution, e.g., by a doctor blade method.
  • the second method for producing the multi-layer, microporous polyolefin membrane comprises the steps of (1) combining (e.g., by melt-blending) a first polyolefin composition and a first membrane-forming solvent to prepare a first polyolefin solution, (2) combining a second polyolefin composition and a second membrane-forming solvent to prepare a second polyolefin solution, (3) extruding the first polyolefin solution through a first die and the second solution through a second die and then laminating the extruded first and second polyolefin solutions to form a multi-layer extrudate, (4) cooling the multi-layer extrudate to form a multi-layer, gel-like sheet, (5) removing at least a portion of the membrane-forming solvent from the multi-layer, gel-like sheet to form a solvent-removed gel-like sheet, and (6) drying the solvent-removed gel-like sheet in order to form the multi-layer, microporous membrane.
  • An optional stretching step (7), and an optional hot solvent treatment step (8), etc., can be conducted between steps (4) and (5), if desired.
  • an optional step (9) of stretching a multi-layer, microporous membrane, an optional heat treatment step (10), an optional cross-linking step with ionizing radiations (11), and an optional hydrophilic treatment step (12), etc. can be conducted.
  • step (3) will be explained in more detail.
  • the type of die used is not critical provided the die is capable of forming an extrudate that can be laminated.
  • sheet dies (which can be adjacent or connected) are used to form the extrudates.
  • the first and second sheet dies are connected to first and second extruders, respectively, where the first extruder contains the first polyolefin solution and the second extruder contains the second polyolefin solution.
  • lamination is generally easier to accomplish when the extruded first and second polyolefin solution are still at approximately the extrusion temperature. The other conditions may be the same as in the first method.
  • first, second, and third sheet dies are connected to first, second and third extruders, where the first and third sheet dies contain the first polyolefin solutions, and the second sheet die contains the second polyolefin solution.
  • a laminated extrudate is formed constituting outer layers comprising the extruded first polyolefin solution and one intermediate comprising the extruded second polyolefin solution.
  • first, second, and third sheet dies are connected to first, second, and third extruders, where the second sheet die contains the first polyolefin solution, and the first and third sheet dies contain the second polyolefin solution.
  • a laminated extrudate is formed constituting outer layers comprising the extruded second polyolefin solution and one intermediate comprising extruded first polyolefin solution.
  • the third method for producing the multi-layer, microporous polyolefin membrane comprises the steps of (1) combining (e.g., by melt-blending) a first polyolefin composition and a membrane-forming solvent to prepare a first polyolefin solution, (2) combining a second polyolefin composition and a second membrane-forming solvent to prepare a second polyolefin solution, (3) extruding the first polyolefin solution through at least one first die to form at least one first extrudate, (4) extruding the second polyolefin solution through at least one second die to form at least one second extrudate, (5) cooling first and second extrudates to form at least one first gel-like sheet and at least one second gel-like sheet, (6) laminating the first and second gel-like sheet to form a multi-layer, gel-like sheet, (7) removing at least a portion of the membrane-forming solvent from the resultant multi-layer, gel-like sheet to form a solvent-removed gel-like sheet
  • An optional stretching step (9), and an optional hot solvent treatment step (10), etc., can be conducted between steps (5) and (6) or between steps (6) and (7), if desired.
  • an optional step (11) of stretching a multi-layer, microporous membrane, an optional heat treatment step (12), an optional cross-linking step with ionizing radiations (13), and an optional hydrophilic treatment step (14), etc. can be conducted.
  • the main difference between the third production method and the second production method is in the order of the steps for laminating and cooling.
  • the first and second polyolefin solutions are cooled before the laminating step.
  • the steps of (1), (2), (7) and (8) in the third production method can be the same as the steps of (1), (2), (5) and (6) in the first production method as described above.
  • the conditions of step (3) of the second production method can be used for step (3) of the third production method.
  • the conditions of step (4) in the third production method can be the same as the conditions of step (3) in the second production method.
  • either the first or second polyolefin solution is extruded through a third die. In this way, a multi-layer laminate can be formed having two layers produced from the first polyolefin solution and a single layer produced from the second polyolefin solution, or vice versa.
  • Step (5) of the third production method can be the same as step (4) in the first production method except that in the third production method the first and second gel-like sheets are formed separately.
  • the step (6) of laminating the first and second gel-like sheets will now be explained in more detail.
  • the choice of lamination method is not particularly critical, and conventional lamination methods such as heat-induced lamination can be used to laminate the multi-layer gel-like sheet.
  • Other suitable lamination methods include, for example, heat-sealing, impulse-sealing, ultrasonic-bonding, etc., either alone or in combination.
  • Heat-sealing can be conducted using, e.g., one or more pair of heated rollers where the gel-like sheets are conducted through at least one pair of the heated rollers.
  • the heat-sealing temperature and pressure are not particularly critical, sufficient heating and pressure should be applied for a sufficient time to ensure that the gel-like sheets are appropriately bonded to provide a multi-layer, microporous membrane with relatively uniform properties and little tendency toward delamination.
  • the heat-sealing temperature can be, for instance, about 90° C. to about 135° C., or from about 90° C. to about 115° C.
  • the heat-sealing pressure can be from about 0.01 MPa to about ⁇ 50 MPa.
  • the thickness of the layers formed from the first and second polyolefin solution i.e., the layers comprising the first and second microporous layer materials
  • the lamination step can be combined with a stretching step by passing the gel-like sheets through multi-stages of heated rollers.
  • the third production method forms a multi-layer, polyolefin gel-like sheet having at least three layers.
  • the multi-layer gel-like sheet can be laminated with outer layers comprising the extruded first polyolefin solution and an intermediate layer comprising the extruded second polyolefin solution.
  • the multi-layer gel-like sheet after cooling two extruded second polyolefin solutions and one extruded first polyolefin solution to form the gel-like sheets, the multi-layer gel-like sheet can be laminated with outer layers comprising the extruded second polyolefin solution and an intermediate layer comprising the extruded first polyolefin solution.
  • the stretching step (9) and the hot solvent treatment step (10) can be the same as the stretching step (7) and the hot solvent treatment step (8) as described for the first production method, except stretching step (9) and hot solvent treatment step (10) are conducted on the first and/or second gel-like sheets.
  • the stretching temperatures of the first and second gel-like sheets are not critical.
  • the stretching temperatures of the first gel-like sheet can be, e.g., Tm 1 +10° C. or lower, or optionally about Tcd 1 or higher but lower than about Tm 1 .
  • the stretching temperature of the second gel-like sheet can be, e.g., Tm 2 +10° C. or lower, or optionally about Tcd 2 or higher but lower than about Tm 2 .
  • the fourth method for producing the multi-layer, microporous polyolefin membrane comprises the steps of (1) combining (e.g., by melt-blending) a first polyolefin composition and a membrane-forming solvent to prepare a first polyolefin solution, (2) combining a second polyolefin composition and a second membrane-forming solvent to prepare a second polyolefin solution, (3) extruding the first polyolefin solution through at least one first die to form at least one first extrudate, (4) extruding the second polyolefin solution through at least one second die to form at least one second extrudate, (5) cooling first and second extrudates to form at least one first gel-like sheet and at least one second gel-like sheet, (6) removing at least a portion of the first and second membrane-forming solvents from the first and second gel-like sheets to form solvent-removed first and second gel-like sheets, (7) drying the solvent-removed first and second gel-like sheets to form at least one first
  • a stretching step (9), a hot solvent treatment step (10), etc., can be conducted between steps (5) and (6), if desired.
  • a stretching step (11), a heat treatment step (12), etc., can be conducted between steps (7) and (8), if desired.
  • a step (13) of stretching a multi-layer, microporous membrane, a heat treatment step (14), a cross-linking step with ionizing radiations (15), a hydrophilic treatment step (16), etc. can be conducted if desired.
  • Steps (1) and (2) in the fourth production method can be conducted under the same conditions as steps of (1) and (2) in the first production method.
  • Steps (3), (4), and (5) in the fourth production method can be conducted under the same conditions as steps (3), (4), and (5) in the third method.
  • Step (6) in the fourth production method can be conducted under the same conditions as step (5) in the first production method except for removing the membrane-forming solvent from the first and second gel-like sheets.
  • Step (7) in the fourth production method can be conducted under the same conditions as step (6) in the first production method except that in the fourth production method the first and second solvent-removed gel-like sheets are dried separately.
  • Step (8) in the fourth production method can be conducted under the same conditions as the step (6) in the third production method except for laminating the first and second polyolefin microporous membranes.
  • the stretching step (9) and the hot solvent treatment step (10) in the fourth production method can be conducted under the same conditions as step (9) and (10) in the third production method.
  • the stretching step (11) and the heat treatment step (12) in the fourth production method can be conducted under the same conditions as steps (9) and (10) in the first production method except that in the fourth production method the first and second polyolefin microporous membranes are stretched and/or heat treated.
  • the stretching temperature of the first polyolefin microporous membranes can be about Tm 1 or lower, or optionally about Tcd 1 to about Tm 1
  • the stretching temperature of the second polyolefin microporous membrane can be about Tm 2 or lower, or optionally about Tcd 2 to about Tm 2 .
  • the heat treatment step (12) in the fourth production method can be HS and/or annealing.
  • the heat-setting temperature of the first polyolefin microporous membranes can be about Tcd 1 to about Tm 1 , or optionally about the dry stretching temperature ⁇ 5° C., or optionally about the dry stretching temperature ⁇ 3° C.
  • the heat-setting temperature of the second microporous membrane can be about Tcd 2 to about Tm 2 , or optionally the dry stretching temperature ⁇ 5° C., or optionally the dry stretching temperature ⁇ 3° C.
  • the HS can be conducted by, e.g., a tenter method or a roller method.
  • the annealing temperature of the first microporous membrane in the heat treatment step (12) in the fourth production method, can be about Tm 1 or lower, or optionally about 60° C. to about (Tm 1 ⁇ 10° C.). In an embodiment, in the heat treatment step (12) in the fourth production method, the annealing temperature of the second microporous membranes can be about Tm 2 or lower, or optionally about 60° C. to about (Tm 2 ⁇ 10° C.).
  • step (13), stretching a multi-layer, microporous membrane, a heat treatment step (14), a cross-linking step with ionizing radiations (15), and a hydrophilic treatment step (16) in the fourth production method can be the same as those for steps (9), (10), (11) and (12) in the first production method.
  • the multi-layer, microporous polyolefin membrane has a thickness ranging from about 3 ⁇ m to about 200 ⁇ m, or about 5 ⁇ m to about 50 ⁇ m.
  • the membrane when it is a multi-layer, microporous polyolefin membrane, it has one or more of the following characteristics.
  • the multi-layer, microporous polyolefin membrane When the porosity is less than 25%, the multi-layer, microporous polyolefin membrane generally does not exhibit the desired air permeability for use as a battery separator. When the porosity exceeds 80%, it is more difficult to produce a battery separator of the desired strength, which can increase the likelihood of internal electrode short-circuiting.
  • the membrane is characterized by or has a least one layer characterized by a hybrid structure, i.e., a relatively broad distribution of differential pore volume as a function of pore diameter.
  • the differential pore volume as a function of pore diameter can have two or more peaks or modes.
  • microporous polyolefin membrane ranges from about 5 g/m 2 to 19 g/m 2 at 25- ⁇ m thickness, the membrane has appropriate porosity.
  • the membrane's normalized air permeability is ⁇ 350 seconds/100 cm 3 , e.g. in the range of 100 seconds/100 cm 3 to 340 seconds/100 cm 3 .
  • the normalized air permeability of the membrane ranges from about 20 seconds/100 cm 3 to about 700 seconds/100 cm 3 , it is less difficult to form batteries having the desired charge storage capacity and desired cyclability.
  • the air permeability is less than about 20 seconds/100 cm 3 , it is more difficult to produce a battery having the desired shutdown characteristics, particularly when the temperatures inside the batteries are elevated.
  • the membrane has Normalized Air Permeability satisfying the relationship A ⁇ (M*P) ⁇ I where A is the microporous membrane's Normalized Air Permeability expressed in units of sec/100 cm 3 and normalized to a 25 ⁇ m membrane thickness and P is the microporous membrane's Normalized Pin Puncture Strength expressed in units of mN and normalized to a 25 ⁇ m membrane thickness.
  • M is a slope (using the axes and units of FIG. 1 ) in the range of about 0.09 to about 0.1, or about 0.95 to about 0.99. In an embodiment, M is equal to 0.097.
  • “I” is an intercept on the Y axis (using the axes and units of FIG.
  • ⁇ 100 e.g., ⁇ 110, such as ⁇ or 150, or ⁇ 200, or ⁇ 250; or, e.g., in the range of about 100 to about 250, such as from about 110 to about 240.
  • the membrane has a Normalized Air Permeability and Normalized Pin Puncture Strength that fall on or within the boundary of the ellipse shown in FIG. 1 .
  • the membrane has an Air Permeability satisfying the relationship (M 2 *P) ⁇ I 2 ⁇ A ⁇ (M 1 *P) ⁇ I 1 .
  • M 1 and M 2 are independently selected and can each be, e.g., in the range of about 0.09 to about 0.1, or about 0.95 to about 0.99. In an embodiment, M 1 and M 2 are equal. For example, M 1 and M 2 can be 0.097; and “I 1 ” can be, e.g., in the range of about 100 to about 240, such as from about 110 to about 230. In an embodiment, I 1 is 110. “I 2 ” can be, e.g., ⁇ 260. For example, I 2 can be in the range of about 260 to about 450. Units and axes are the same as in FIG. 1 .
  • the pin puncture strength (normalized to the value at a 25- ⁇ m membrane thickness) is the maximum load measured when the multi-layer, microporous polyolefin membrane is pricked with a needle 1 mm in diameter with a spherical end surface (radius R of curvature: 0.5 mm) at a speed of 2 mm/second.
  • the pin puncture strength of the multi-layer, microporous polyolefin membrane is less than 3,000 mN/25 ⁇ m, it is more difficult to produce a battery having the desired mechanical integrity, durability, and toughness.
  • the membrane's Normalized Pin Puncture strength is in the range of 4500 mN/25 ⁇ to 600 mN/25 g.
  • the membrane's heat shrinkage at 105° C. is in the range of 1% to 5% (MD) and 1% to 5% (TD), such as 1% to 3% (TD).
  • shutdown temperature When the shutdown temperature of the multi-layer, microporous polyolefin membrane exceeds 140° C., it is more difficult to produce a battery separator with the desired shutdown response when the battery is overheated.
  • One way to determine shutdown temperature involves determining the temperature at a point of inflection observed near the melting point of the multi-layer, microporous polyolefin membrane, under the condition that a test piece of 3 mm in the longitudinal direction and 10 mm in the transverse direction is heated from room temperature at a speed of 5° C./minute while drawing the test piece in the longitudinal direction under a load of 2 g.
  • the shutdown temperature is in the range of about 120-140° C.
  • the microporous membrane should have a rupture temperature of about 180° C. or higher, or about 185° C. or higher, or about 190° C. or higher. In an embodiment, the rupture temperature is in the range of about 180° C. to about 195° C., or about 185° C. to about 190° C.
  • Rupture temperature can be measured as follows. A microporous membrane of 5 cm ⁇ 5 cm is sandwiched by blocks each having a circular opening of 12 mm in diameter, and a tungsten carbide ball of 10 mm in diameter was placed on the microporous membrane in the circular opening.
  • FIG. 2 shows that when the total amount polypropylene in the membrane is 2 wt. % or higher, based on the total weight of the membrane, the membrane's Rupture temperature 180° C. or higher.
  • the total amount polypropylene in the membrane having
  • the multi-layer microporous membrane should exhibit a maximum shrinkage in the molten state (about 140° C.) of about 30% or less, preferably about 20% or less as measured by a thermomechanical analyzer, (“TMA”).
  • TMA thermomechanical analyzer
  • the battery separator formed by the above multi-layer, microporous polyolefin membrane has a thickness in the range of about 3 ⁇ m to about 200 ⁇ m, or about 5 ⁇ m to about 50 ⁇ m.
  • separator swelling might increase the final thickness to a value larger than 200 ⁇ m.
  • the multi-layer, microporous polyolefin membrane can be used as a separator for primary and secondary batteries such as lithium ion batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, and particularly for lithium ion secondary batteries.
  • primary and secondary batteries such as lithium ion batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, and particularly for lithium ion secondary batteries.
  • primary and secondary batteries such as lithium ion batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver-zinc secondary batteries, and particularly for lithium ion secondary batteries.
  • the lithium secondary battery comprises a cathode, an anode, and a separator located between the anode and the cathode.
  • the separator generally contains an electrolytic solution (electrolyte).
  • the electrode structure is not critical, and conventional electrode structures can be used.
  • the electrode structure may be, for instance, a coin type in which a disc-shaped cathode and anode are opposing, a laminate type in which a planar cathode and anode are alternately laminated with at least one separator situated between the anode and the cathode, a toroidal type in which ribbon-shaped cathode and anode are wound, etc.
  • the cathode generally comprises a current collector, and a cathodic-active material layer capable of absorbing and discharging lithium ions, which is formed on the current collector.
  • the cathodic-active materials can be, e.g., inorganic compounds such as transition metal oxides, composite oxides of lithium and transition metals (lithium composite oxides), transition metal sulfides, etc.
  • the transition metals can be, e.g., V, Mn, Fe, Co, Ni, etc.
  • the lithium composite oxides are lithium nickelate, lithium cobaltate, lithium manganate, laminar lithium composite oxides based on ⁇ -NaFeO 2 , etc.
  • the anode generally comprises a current collector, and a negative-electrode active material layer formed on the current collector.
  • the negative-electrode active materials can be, e.g., carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, etc.
  • the electrolytic solutions can be obtained by dissolving lithium salts in organic solvents.
  • the choice of solvent and/or lithium salt is not critical, and conventional solvents and salts can be used.
  • the lithium salts can be, e.g., LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , Li 2 B 10 Cl 10 , LiN(C 2 F 5 SO 2 ) 2 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , lower aliphatic carboxylates of lithium, LiAlCl 4 , etc.
  • the lithium salts may be used alone or in combination.
  • the organic solvents can be organic solvents having relatively high boiling points (compared to the battery's shut-down temperature) and high dielectric constants. Suitable organic solvents include ethylene carbonate, propylene carbonate, ethylmethyl carbonate, ⁇ -butyrolactone, etc.; organic solvents having low boiling points and low viscosity such as tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dioxolane, dimethyl carbonate, diethyl carbonate, and the like, including mixtures thereof. Because the organic solvents generally having high dielectric constants generally also have a high viscosity, and vice versa, mixtures of high- and low-viscosity solvents can be used.
  • the separator When the battery is assembled, the separator is generally impregnated with the electrolytic solution, so that the separator (multi-layer, microporous membrane) is provided with ion permeability.
  • the choice of impregnation method is not critical, and conventional impregnation methods can be used.
  • the impregnation treatment can be conducted by immersing the multi-layer, microporous membrane in an electrolytic solution at room temperature.
  • the method selected for assembling the battery is not critical, and conventional battery-assembly methods can be used.
  • a cathode sheet, a separator formed by the multi-layer, microporous membrane and an anode sheet are laminated in this order, and the resultant laminate is wound to a toroidal-type electrode assembly.
  • a second separator might be needed to prevent short-circuiting of the toroidal windings.
  • the resultant electrode assembly can be deposited into a battery can and then impregnated with the above electrolytic solution, and a battery lid acting as a cathode terminal provided with a safety valve can be caulked to the battery can via a gasket to produce a battery.
  • a first polyolefin composition comprising (a) 80% of PE1 having a weight average molecular weight of 5.6 ⁇ 10 5 and a molecular weight distribution of 4.05, (b) 20% of PE2 having a weight average molecular weight of 1.9 ⁇ 10 6 and a molecular weight distribution of 5.09, is prepared by dry-blending.
  • the polyethylene composition has a melting point of 135° C. and a crystal dispersion temperature of 100° C.
  • first polyolefin composition Twenty-five parts by weight of the resultant first polyolefin composition is charged into a strong-blending double-screw extruder having an inner diameter of 58 mm and L/D of 42, and 65 parts by mass of liquid paraffin (50 cst at 40° C.) is supplied to the double-screw extruder via a side feeder. Melt-blending is conducted at 210° C. and 200 rpm to prepare a first polyolefin solution.
  • a second polyolefin solution is prepared in the same manner as above except as follows.
  • a second polyolefin composition comprising (a) 69% of PE1 having a weight average molecular weight of 5.6 ⁇ 10 5 and a molecular weight distribution of 4.05, and (b) 1% of PE2 having a weight average molecular weight of 1.9 ⁇ 10 6 and a molecular weight distribution of 5.09, and (c) 30% of polypropylene resin having a weight average molecular weight of 1.6 ⁇ 10 6 , a molecular weight distribution of 5.21 and a heat of fusion of 114.0 J/g, by weight of the second polyolefin composition, is prepared by dry-blending.
  • the polyolefin composition has a melting point of 135° C.
  • the first and second polyolefin solutions are supplied from their respective double-screw extruders to a three-layer-extruding T-die, and extruded therefrom to form an extrudate (also called a laminate) of first polyolefin solution layer/second polyolefin solution layer/first polyolefin solution layer at a layer thickness ratio of 46/8/46.
  • the extrudate is cooled while passing through cooling rollers controlled at 20° C., to form a three-layer gel-like sheet, which is simultaneously biaxially stretched at 115° C. to a magnification of 5 fold in both machine (longitudinal) and transverse directions by a tenter-stretching machine.
  • the stretched three-layer gel-like sheet is fixed to an aluminum frame of 20 cm ⁇ 20 cm, immersed in a bath of methylene chloride controlled at 25° C. to remove liquid paraffin with vibration of 100 rpm for 3 minutes, and dried by air flow at room temperature.
  • the dried membrane is re-stretched by a batch-stretching machine to a magnification of 1.4 fold in a transverse direction at 127° C.
  • the re-stretched membrane which remains fixed to the batch-stretching machine, is heat-set at 127° C. for 10 minutes to produce a three-layer microporous membrane.
  • Example 1 is repeated except the dried membrane is re-stretched to a magnification of 1.6 fold in a transverse direction at 127° C. and contracted to a magnification of 1.4 fold in the direction at 127° C. compared with original size.
  • Example 1 is repeated except the first polyolefin content in the first polyolefin solution is 25%, the second polyolefin composition comprises (a) 64% of PE1, (b) 1% of PE2 and (c) 35% of the second polypropylene, a layer thickness ratio of first microporous membrane/second microporous membrane/first microporous membrane is 47/6/47, the gel-like sheet is stretched at 119° C. and the dried membrane is re-stretched to a magnification of 1.5 fold in a transverse direction at 127° C. and shrank to a magnification of 1.3 fold in the direction at 127° C.
  • Example 3 is repeated except the second polyolefin composition comprises (a) 49% of PE1, (b) 1% of PE2 and (c) 50% of the second polypropylene, a layer thickness ratio of first microporous membrane/second microporous membrane/first microporous membrane is 46/8/46, the gel-like sheet is stretched at 115° C.
  • Example 4 is repeated except the second polyolefin comprises (a) 79% of PE1, (b) 1% of PE2, and (c) 20% of second polypropylene and a layer thickness ratio of first microporous membrane/second microporous membrane/first microporous membrane is 35/30/35.
  • Example 4 is repeated except a layer thickness ratio of first microporous membrane/second microporous membrane/first microporous membrane is 40/20/40.
  • Example 2 is repeated except the first polyolefin content in the first polyolefin solution is 25% and the second polypropylene resin in the second polyolefin composition has a weight average molecular weight of 0.90 ⁇ 10 6 , a molecular weight distribution of 4.5 and a heat of fusion of 106.0 J/g.
  • Example 7 is repeated except the first polyolefin composition comprises (a) 80% of PE1, (b) 12% of PE2 and (c) 8% of the first polypropylene having a weight average molecular weight of 6.6 ⁇ 10 5 , a molecular weight distribution of 1 and a heat of fusion of 103.3 J/g.
  • Example 1 is repeated except there is no second polyolefin solution.
  • the membrane is a monolayer membrane produced from the first polyolefin solution.
  • This comparative example also differs from Example 1 in that the dried membrane is not re-stretched.
  • Example 2 is repeated except there is no first polyolefin solution.
  • the membrane is a monolayer membrane produced from the second polyolefin solution.
  • Example 2 is repeated except the first polyolefin content in the first polyolefin solution is 25% and a layer thickness ratio of first microporous membrane/second microporous membrane/first microporous membrane is 47/6/47.
  • Example 2 is repeated except the second polypropylene resin in the second polyolefin composition has a weight average molecular weight of 0.54 ⁇ 10 6 , a molecular weight distribution of 4.7 and a heat of fusion of 94.0 J/g.
  • Example 2 is repeated except the second polypropylene resin in the second polyolefin composition has a weight average molecular weight of 1.56 ⁇ 10 6 , a molecular weight distribution of 3.2 and a heat of fusion of 78.40 J/g.
  • Example 2 is repeated except the second polypropylene resin in the second polyolefin composition has a weight average molecular weight of 2.67 ⁇ 10 6 , a molecular weight distribution of 2.6 and a heat of fusion of 99.4.
  • each microporous membrane is measured by a contact thickness meter at 10 mm intervals in the area of 10 cm ⁇ 10 cm of the membrane, and averaged.
  • the thickness meter used is a Litematic made by Mitsutoyo Corporation.
  • Porosity % 100 ⁇ (w2 ⁇ w1)/w2, wherein “w1” is the actual weight of film and “w2” is the assumed weight of 100% polyethylene.
  • a weight per unit area of the membrane is the weight at 1 square meter and calculated based on the weight of above square membrane.
  • the maximum load is measured when each microporous membrane having a thickness of T 1 is pricked with a needle of 1 mm in diameter with a spherical end surface (radius R of curvature: 0.5 mm) at a speed of 2 mm/second.
  • the shrinkage ratios of each microporous membrane in both longitudinal and transverse directions are measured three times when exposed to 105° C. for 8 hours, and averaged to determine the heat shrinkage ratio.
  • the shut down temperature is measured as follows: A rectangular sample of 3 mm ⁇ 50 mm is cut out of the microporous membrane such that the longitudinal direction of the sample is aligned with the transverse direction of the microporous membrane, and set in a thermomechanical analyzer (TMA/SS6000 available from Seiko Instruments, Inc.) at a chuck distance of 10 mm. With a load of 19.6 mN applied to a lower end of the sample, the temperature is elevated at a rate of 5° C./minute to measure its size change. A temperature at a point of inflection observed near the melting point is defined as the shutdown temperature.
  • TMA/SS6000 thermomechanical analyzer
  • a microporous membrane of 5 cm ⁇ 5 cm is sandwiched by blocks each having a circular opening of 12 mm in diameter, and a tungsten carbide ball of 10 mm in diameter was placed on the microporous membrane in the circular opening. While heating at a temperature-elevating speed of 5° C./minute, the temperature at which the microporous polyolefin membrane is ruptured by melting is measured and recorded as the Rupture temperature.
  • the maximum shrinkage in the molten state is measured as follows: A rectangular sample of 3 mm ⁇ 50 mm is cut out of the microporous membrane such that the longitudinal direction of the sample is aligned with the transverse direction of the microporous membrane, and set in a thermomechanical analyzer (TMA/SS6000 available from Seiko Instruments, Inc.) at a chuck distance of 10 mm. With a load of 19.6 mN applied to a lower end of the sample, the temperature is elevated at a rate of 5° C./minute to measure the membrane sample's size change. A size change ratio is calculated relative to the size at 23° C., to obtain a temperature-size change ratio curve. The maximum shrinkage ratio in the molten state is observed in a temperature range of from 135° C. to 145° C.
  • microporous membrane of the present invention has well-balanced properties, including air permeability, pin puncture strength, shut down temperature and rupture down temperature, as well as low maximum shrinkage in the molten state.
  • Lithium ion secondary batteries comprising the microporous membranes of the present invention have high capacity and high safety performance. As discussed in the Background, the selection of polymer type and content for microporous polymeric membranes represents a trade-off.
  • Polymeric materials and membrane structures that conventionally provide a relatively high porosity (or high Air Permeability as characterized by a shorter time to pass a volume of air through the pores of the membrane) generally lead to a lower membrane Pin Puncture Strength, particularly when a relatively high Rupture temperature is desired, e.g., 180° C. or higher.
  • the invention is based in part on the discovery that three-layer membranes as described above exemplified in the Examples 1 through 8 achieve an optimization of Air Permeability, Pin Puncture Strength, and Rupture temperature.
  • the microporous membranes of the Comparative Examples exhibit a poorer balance of these properties.
  • Comparative Examples 3, 4, and 5 have an Air Permeability satisfying the relationship A ⁇ 0.097P-110, they do not have a meltdown temperature in the range of 180° C. or higher.
  • microporous membranes of the present invention have well-balanced properties and the of such microporous membrane as a battery separator provides batteries having excellent safety, heat resistance and productivity.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
US12/741,187 2007-11-30 2008-11-17 Microporous Polymeric Membrane, Battery Separator, and Battery Abandoned US20100297491A1 (en)

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US20080118827A1 (en) * 2006-11-17 2008-05-22 Call Ronald W Co-extruded, multi-layered battery separator
US8012622B2 (en) * 2007-11-14 2011-09-06 Toray Tonen Specialty Separator Godo Kaisha Multi-layer, microporous membrane, battery separator and battery
US20110003178A1 (en) * 2007-11-30 2011-01-06 Takeshi Ishihara Microporous Films, Methods for Their Production, and Applications Thereof

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US20110206973A1 (en) * 2008-10-24 2011-08-25 Toray Tonen Specialty Separator Godo Kaisha Multi-layer microporous membranes and methods for making and using such membranes
US20130288102A1 (en) * 2010-12-22 2013-10-31 Toray Battery Separator Film Co., Ltd. Microporous film, methods for making such film, and use for such film as battery separator film
US9502705B2 (en) * 2010-12-22 2016-11-22 Toray Battery Separator Film Co., Ltd. Microporous film, methods for making such film, and use for such film as battery separator film
US20150005405A1 (en) * 2011-12-28 2015-01-01 Toray Battery Separator Film Co., Ltd. Polyolefin microporous film and method for producing same
US9624349B2 (en) * 2011-12-28 2017-04-18 Toray Battery Separator Film Co., Ltd. Polyolefin microporous film and method for producing same
US9911956B2 (en) 2011-12-28 2018-03-06 Toray Industries, Inc. Polyolefin microporous film and method of producing same
US10340491B2 (en) * 2013-01-31 2019-07-02 Samsung Sdi Co., Ltd. Method for manufacturing separation film and the separation film, and battery using same
US20180301776A1 (en) * 2017-04-13 2018-10-18 Toyota Motor Engineering & Manufacturing North America, Inc. Lithium air battery
US11189870B2 (en) * 2017-04-13 2021-11-30 Toyota Motor Engineering & Manufacturing North America, Inc. Lithium air battery

Also Published As

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EP2227387B1 (fr) 2013-07-17
WO2009069534A2 (fr) 2009-06-04
WO2009069534A3 (fr) 2009-09-24
ES2428094T3 (es) 2013-11-05
US20130309548A1 (en) 2013-11-21
CN101878109A (zh) 2010-11-03
JP2011505266A (ja) 2011-02-24
US9147868B2 (en) 2015-09-29
CN101878109B (zh) 2016-03-09
KR20100075663A (ko) 2010-07-02
JP4940351B2 (ja) 2012-05-30
WO2009069533A1 (fr) 2009-06-04
EP2227387A1 (fr) 2010-09-15
US20110003178A1 (en) 2011-01-06

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