Improved micro-layer membranes, improved battery separators, and related methods

Abstract

Described are multi-layer microporous films or membranes that can exhibit improved properties, including improved dielectric breakdown and strength, compared to existing single-layer or triple-layer microporous membranes of the same thickness. Preferred multi-layer microporous membranes comprise a micron layer and one or more laminated barriers. Also disclosed are battery separators or batteries comprising one or more multi-layer microporous films or membranes. The batteries and battery separators of the present invention are preferably safer and stronger than batteries and battery separators using existing single-layer and triple-layer microporous membranes. In addition, methods of making the multi-layer microporous separators, membranes or films described herein are described.

Description

[0001] Priority declaration

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 62 / 508,360, filed May 18, 2017, and U.S. Provisional Application No. 62 / 420,781, filed November 11, 2016, pursuant to 35 USC §119(e)(1). Each of these provisional applications is hereby incorporated by reference in its entirety. Field of the Invention

[0003] According to at least selected embodiments, the present application, disclosure or invention relates to a new or improved membrane, separator membrane, separator, battery separator, secondary lithium battery separator, multilayer membrane, multilayer separator membrane, multilayer separator, multilayer battery separator, multilayer secondary lithium battery separator and / or multilayer battery separator with improved performance, a new or improved battery, capacitor, fuel cell, lithium battery, lithium ion battery, secondary lithium battery and / or secondary lithium ion battery and / or a method of manufacturing and / or using such a membrane, separator membrane, separator, battery separator, secondary lithium battery separator, battery, capacitor, fuel cell, lithium battery, lithium ion battery, secondary lithium battery and / or secondary lithium ion battery and / or a device, vehicle or product comprising it. According to at least specific embodiments, the present disclosure or invention relates to a new or improved membrane layer, membrane or separator membrane, a battery separator comprising such a membrane and / or a related method. According to at least specific selected embodiments, the present disclosure or invention relates to a new or improved porous polymer membrane or separator membrane, a battery separator comprising such a membrane and / or a related method. According to at least a particular embodiment, the present disclosure or invention relates to a new or improved microporous polyolefin film or separator film, a microlayer film, a multilayer film including one or more microlayers or nanolayer films, a battery separator including such a film, and / or related methods. According to at least a particular particular embodiment, the present disclosure or invention relates to a new, optimized or improved microporous stretched polymer film or separator film, a microlayer film, a multilayer microporous film or separator film having an outer layer and an inner layer, wherein some layers or sublayers are produced by coextrusion and subsequently laminated together to form a new, optimized or improved film or separator film. In some embodiments, a particular layer, microlayer or nanolayer may comprise a homopolymer, a copolymer, a block copolymer, an elastomer and / or a polymer blend. In a selected embodiment, at least a particular layer, microlayer or nanolayer may comprise a different or different polymer, homopolymer, copolymer, block copolymer, elastomer and / or polymer blend. The present disclosure or invention also relates to new or improved methods of making such films, separator films or separators, and / or methods of using such films, separator films or separators, for example as lithium battery separators. According to at least selected embodiments, the present application or invention is directed to new or improved multilayer and / or micron-layer porous or microporous films, separator films, separators, composites, electrochemical devices and / or batteries and / or methods of making and / or using such films, separators, composites, devices and / or batteries. According to at least particularly selected embodiments, the present application or invention is directed to multilayer new or improved separator films, wherein one or more layers of the multilayer structure are made in a multilayer or micron-layer coextrusion die with multiple extruders. The new or improved film, separator film or separator may preferably exhibit improved shutdown, improved strength, improved dielectric breakdown strength and / or reduced cracking tendency. Background of the Invention

[0005] Known methods for making microporous bilayer or trilayer films such as those used as battery separator films include laminating or bonding two or more monolayer precursors together, or coextruding multiple layers of the film simultaneously using a coextrusion die. These methods are described, for example, in US5,952,120, US2014 / 0079980, US5,223,032, US5,240,655, and US2005 / 031943.

[0006] For applications such as for certain primary and / or secondary batteries (e.g., lithium-ion rechargeable batteries), the above approach may not fully optimize the balance between strength and / or performance characteristics. This is particularly true as battery separator requirements are becoming increasingly demanding as customers demand thinner and stronger battery separators. For example, a microporous three-layer membrane formed by coextruding three layers may have reduced strength. Separators formed by laminating multiple single layers may also ultimately fail to meet the growing demand.

[0007]

[0006] Therefore, there is a need for a new and improved multi-layer microporous membrane, base membrane or battery separator having various improvements, such as improved tensile strength and improved dielectric breakdown strength. SUMMARY OF THE INVENTION

[0009] According to at least selected embodiments, the present application, disclosure or invention can solve the above-mentioned needs, problems or difficulties and / or can provide new or improved membranes, separator membranes, separators, battery separators, secondary lithium battery separators, multilayer membranes, multilayer separator membranes, multilayer separators, multilayer battery separators, multilayer secondary lithium battery separators and / or multilayer battery separators with improved performance, new or improved batteries, capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries and / or secondary lithium ion batteries and / or methods of manufacturing and / or using such membranes, separator membranes, separators, battery separators, secondary lithium battery separators, batteries, capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries and / or secondary lithium ion batteries and / or devices, vehicles or products including them. According to at least specific embodiments, the present disclosure or invention relates to new or improved membrane layers, membranes or separator membranes, battery separators including such membranes and / or related methods. According to at least specific selected embodiments, the present disclosure or invention relates to new or improved porous polymer membranes or separator membranes, battery separators including such membranes and / or related methods. According to at least a particular embodiment, the present disclosure or invention relates to a new or improved microporous polyolefin film or separator film, a microlayer film, a multilayer film including one or more microlayers or nanolayer films, a battery separator including such a film, and / or related methods. According to at least a particular particular embodiment, the present disclosure or invention relates to a new, optimized or improved microporous stretched polymer film or separator film, a microlayer film, a multilayer microporous film or separator film having an outer layer and an inner layer, wherein some layers or sublayers are produced by coextrusion and then laminated together to form a new, optimized or improved film or separator film. In some embodiments, a specific layer, microlayer or nanolayer may comprise a homopolymer, a copolymer, a random copolymer, a PP and / or PE copolymer, a block copolymer, an elastomer and / or a polymer blend. In a selected embodiment, at least a specific layer, microlayer or nanolayer may comprise a different or different polymer, homopolymer, copolymer, block copolymer, elastomer and / or polymer blend. The present disclosure or invention also relates to new or improved methods of making such films, separator films or separators, and / or methods of using such films, separator films or separators, for example as lithium battery separators. According to at least selected embodiments, the present application or invention is directed to new or improved multilayer and / or micron-layer porous or microporous films, separator films, separators, composites, electrochemical devices and / or batteries and / or methods of making and / or using such films, separators, composites, devices and / or batteries. According to at least particularly selected embodiments, the present application or invention is directed to multilayer new or improved separator films, wherein one or more layers of the multilayer structure are made in a multilayer or micron-layer coextrusion die with multiple extruders. The new or improved film, separator film or separator may preferably exhibit improved shutdown, improved strength, improved dielectric breakdown strength and / or reduced cracking tendency.

[0010] In some embodiments, the microporous multilayer battery separators described herein exhibit improved safety, strength, and durability compared to existing two-layer, three-layer, or multi-layer battery separators. For example, the separators may exhibit increased average dielectric breakdown (DB), increased minimum DB, increased closing speed, and increased bending, all of which indicate that the battery separators are safer. The separators may also exhibit increased puncture strength and increased hybrid penetration values, indicating that the battery is stronger and more durable.

[0011] These properties of the microporous multilayer battery separators described herein are at least in part the result of the method of making them. In some embodiments, the method includes at least coextruding two or more polymer mixtures to form a first coextruded two-layer, three-layer or multilayer film; coextruding two or more other polymer mixtures to form a second coextruded two-layer, three-layer or multilayer film; and coextruding two or more other polymer mixtures to form a third coextruded two-layer, three-layer or multilayer film. Coextrusion generally involves the use of a coextrusion die having one or more extruders feeding the die (usually one extruder for each layer of the two-layer, three-layer or multilayer film). The polymer mixture used to form each layer of the first, second and third two-layer, three-layer or multilayer film may be the same or different. The mixture may contain only one polymer or multiple polymers, such as a polymer blend. Moreover, more than three two-layer, three-layer or multilayer films may be formed. After forming the first, second and third two-layer, three-layer or multilayer films, the film is laminated with two film layers formed on the opposite surface of one of the films to form a microporous battery separator that may be preferred as described herein.

[0012] The microporous multilayer battery separators described herein can be used in lithium ion batteries, including secondary lithium batteries, resulting in batteries with improved safety and durability.

[0013] The battery separators herein can be described in several different ways.

[0014] In a first aspect, a battery separator for a lithium battery is described herein. In some embodiments, the battery separator comprises at least one microporous separator membrane or sublayer membrane, which comprises a plurality of porous or microporous polymer microlayers or nanolayers, wherein at least one individual microlayer or nanolayer comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend, comprises different or different additives, reagents, materials and / or fillers compared to an adjacent individual microlayer or nanolayer, or comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer, random copolymer of ethylene and / or propylene, polymer blend, additive, reagent, material, elastomer, SEPS, SEBS, PVDF, EVOH, PMP, filler, particle, ceramic particle, bead, fiber, detergent, crosslinking agent, adhesion promoter, combination of surface modifiers and / or combinations thereof. In some embodiments, a plurality of separator membranes or sublayers of polymer microlayers or nanolayers are laminated to each other or laminated to a microporous polymer membrane. In some embodiments, at least one of the separator films or sub-layer films of polymer micro-layers or nano-layers has at least three micro-layers or nano-layers. Sometimes, at least one of the separator films or sub-layer films of polymer micro-layers or nano-layers is made of one or more polyolefins. Sometimes, at least one of the separator films or sub-layer films of polymer micro-layers or nano-layers is composed of co-extruded dry process polyolefin micro-layers or nano-layers. In some embodiments, at least two of the separator films or sub-layer films of polymer micro-layers or nano-layers. In some embodiments, at least three of the separator films or sub-layer films of polymer micro-layers or nano-layers.

[0015] In another aspect, described herein is a lithium battery comprising any of the battery separators described directly above.

[0016] In another aspect, an improved separator, membrane or base film is described herein. In some embodiments, the separator is a multilayer separator, membrane or base film comprising one or more microporous coextruded multilayer microlayer or multilayer nanolayer polymer film or sublayer film, which is suitable for lamination or bonding with another polymer film, wherein at least one individual microlayer or nanolayer comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend, comprises different or different additives, agents, materials and / or fillers, or comprises a combination of different or different polymers, molecular weight polymers, homopolymers, copolymers, polymer blends, additives, agents, materials and / or fillers compared to an adjacent individual microlayer or nanolayer.

[0017] In another aspect, described herein is a battery comprising at least one battery separator as described in the preceding paragraph.

[0018] In one other aspect, a battery separator or separator film is described herein. In some embodiments, the battery separator or separator film comprises one or more coextruded multi-layer microlayer films laminated or bonded to another polymer film, wherein the separator or separator film can provide improved strength, for example, improved puncture strength, particularly at a particular thickness, and can exhibit improved shutdown and / or reduced cracking tendency, and wherein at least one individual microlayer comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend, comprises different or different additives, agents, materials and / or fillers, or comprises a combination of different or different polymers, molecular weight polymers, homopolymers, copolymers, polymer blends, additives, agents, materials and / or fillers compared to adjacent individual microlayers.

[0019] In another aspect, described herein is a battery, in particular a lithium-ion battery comprising at least one separator as described in the preceding paragraph.

[0020] In another aspect, a battery separator or separator film is described herein. The battery separator or separator film comprises, in some embodiments, one or more coextruded multi-layer micro-layer or multi-layer nano-layer films optionally laminated or bonded to another polymer film. The separator or separator film may exhibit improved strength, improved puncture strength, particularly at a particular thickness, and / or may exhibit improved closure and / or reduced cracking tendency. In some embodiments, at least one individual micro-layer or nano-layer comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend, comprises different or different additives, agents, materials and / or fillers, or comprises a combination of different or different polymers, molecular weight polymers, homopolymers, copolymers, polymer blends, additives, agents, materials and / or fillers compared to an adjacent individual micro-layer or nano-layer.

[0021] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0022] In another aspect, an improved battery separator comprising a multilayer microporous film is described herein. In some embodiments, the multilayer microporous film comprises 9 or more layers, 12 or more layers, 15 or more layers, 18 or more layers, 21 or more layers, 24 or more layers, 27 or more layers, 30 or more layers, or more layers. In some embodiments, the thickness of at least three continuous layers of the microporous film is 0.1 to 5 microns, 0.1 to 3 microns, 0.1 to 2.5 microns, or 0.1 to 2.0 microns. In some embodiments, the battery separator itself has a thickness of 1 micron to 30 microns, 2 microns to 20 microns, 3 microns to 15 microns, or 4 microns to 10 microns. In some embodiments, at least three continuous layers each independently comprise a polyolefin or a polyolefin blend; in some embodiments, each of them comprises polyethylene, and in some embodiments, each of them comprises polypropylene.

[0023] In some cases, at least three continuous layers are coextruded layers. In some embodiments, these at least three continuous layers are laminated with at least one other layer to form a microporous polymer film. In some embodiments, this at least one other layer is also a coextruded layer, which is coextruded with at least one other layer. The battery separator of claim 28, wherein at least one other layer is a coextruded layer. In some embodiments, the battery separator has a puncture strength of 290 gf or more, 300 gf or more, or 310 gf or more.

[0024] In another aspect, described herein are batteries, including lithium ion batteries, particularly lithium ion secondary batteries, comprising one or more battery separators as described in the preceding paragraphs. The batteries are at least more durable, particularly in embodiments where the battery separator has a puncture strength of 290 gf or more, 300 gf or more, or 310 gf or more.

[0025] In yet another aspect, a microporous multilayer battery separator is described herein. The battery separator includes a first region comprising two or more layers and a second region comprising at least one layer, wherein when viewed along the Z direction of the film using an SEM, the first region mainly comprises a non-continuous amorphous region. In some embodiments, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of the amorphous region in the first region is non-continuous. In some embodiments, the second region comprises two or more layers, preferably three or more layers, and the amorphous region has a maximum width of 0.8 microns, a maximum width of 0.7 microns, or a maximum width of 0.6 microns. In some embodiments described herein, at least one of the first and second regions comprises one or more layers containing polyolefins. In some embodiments, the first region comprises at least one layer containing polyethylene, and the second region comprises at least one layer containing polypropylene. Sometimes, at least one of the first region and the second region comprises a coextruded two-layer, three-layer or multilayer film. Sometimes, the first region comprises a coextruded two-layer, three-layer or multilayer film. Sometimes, the first region comprises a coextruded two-layer, three-layer or multilayer film. Sometimes, the first region and the second region comprise a coextruded two-layer, three-layer or multilayer film. Sometimes, the first region, the second region, and the third region of the microporous multilayer battery separator each comprise a coextruded two, three, or more layers of film. Sometimes, at least one of the second and third regions of the microporous multilayer battery separator comprises a coextruded two, three, or more layers of film. Sometimes, the second region comprises a coextruded two, three, or more layers of film. Sometimes, the third region comprises a coextruded two, three, or more layers of film.

[0026] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0027] On the other hand, a battery separator comprises a multilayer microporous film having an average dielectric breakdown (DB) value higher than the average dielectric breakdown value of a typical three-layer microporous film having at least one of the same thickness, Gurley value, and porosity as the multilayer microporous film. For example, the average DB value may be 1 to 35% higher, 5 to 35% higher, 10 to 35% higher, 15 to 35% higher, or 20 to 35% higher. In some embodiments, the DB minimum value of the microporous multilayer film of the battery separator described herein may be higher than the DB minimum value of a typical or conventional three-layer microporous film having the same thickness, Gurley value, and / or porosity as the multilayer microporous film. For example, it may be 3 to 20%, 5 to 15%, or 10 to 15% higher than the DB minimum value of a three-layer microporous film having the same thickness, Gurley value, and / or porosity as the multilayer microporous film. Sometimes, the multilayer microporous film comprises 9 or more layers, 12 or more layers, 15 or more layers, 18 or more layers, 21 or more layers, 24 or more layers, 27 or more layers, or 30 or more layers. In some embodiments, at least one layer comprises a polyolefin or a polyolefin blend. The polyolefin blend can be polyethylene or a polyethylene blend or polypropylene or a polypropylene blend. In some other embodiments, the multilayer microporous film having the dielectric breakdown value described herein may comprise a first region comprising two or more layers and a second region comprising at least one layer. When observed in the Z direction of the film using SEM, the first region may comprise polypropylene and is mainly a discontinuous amorphous region. In some embodiments, the multilayer microporous film having a battery separator with improved dielectric breakdown described herein may comprise the following: (1) a first region comprising two or more layers, a second region comprising at least one layer, and a third region comprising at least one layer. When observed in the Z direction (or thickness direction) of the film using SEM, the first region may comprise polypropylene and is mainly a discontinuous amorphous region.

[0028] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0029] In another aspect herein, a battery separator comprising a multi-layer microporous film exhibits a log differential mercury intrusion value of 5 mL / g or less, 4.5 mL / g or less, 4 mL / g or less, or 3.5 mL / g or less at a pressure sufficient to allow mercury to fill the pores, as measured by mercury intrusion porosimetry.

[0030] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0031] In another aspect, a battery separator comprising a multi-layer microporous film having a MacMillan number greater than 5, greater than 5.5, greater than 6, greater than 6.5, greater than 7, greater than 8, greater than 9, or greater than 10 is described herein.

[0032] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0033] In another aspect of the present invention, a battery separator comprising a multi-layer microporous film having a curvature value of 1.6 or more, 1.8 or more, or 2.0 or more is described herein. In some embodiments, the battery separator herein is a microporous battery separator. In some embodiments, the battery separator is a microporous multi-layer battery separator.

[0034] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0035] In another aspect, a battery separator comprising a multi-layer microporous film exhibits a pin removal force of less than 50 Newtons, 40 Newtons, 30 Newtons, 20 Newtons, 15 Newtons, or 10 Newtons.

[0036] In another aspect, a battery, particularly a lithium ion battery, comprising at least one membrane or separator as described in the preceding paragraph is described herein. It may be preferred that the membrane or separator is a dry process or dry stretch process polyolefin based film, particularly a blown or bubble extruded MD stretch or MD+TD stretch film, but other films such as slot die extrusion or casting, wet process, BNBOPP, BOPP, pellet stretch and / or the like may also be used. For example, a dry process multilayer PO film may be laminated with a BNBOPP film.

[0037] In another aspect, a battery separator is described herein. The battery separator comprises a microporous multilayer film comprising: (1) a first region comprising two or more layers; (2) a second region comprising two or more layers located on a first side of the first region; and (3) a third region comprising two or more layers located on a side opposite the first side of the first region, wherein at least one of the first, second, or third regions comprises PE and has a lower crystallinity than the PE-containing layer of a three-layer microporous film when measured by DSC, wherein the three-layer microporous film has the same thickness as the multilayer microporous film. For example, the crystallinity can be 1 to 20% lower, 1 to 15% lower, 1 to 10% lower, or 1 to 5% lower.

[0038] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0039] In another aspect, described herein are battery separators comprising a multi-layer microporous film having a mixed permeability (N) value greater than 380N, greater than 400N, greater than 450N, greater than 500N, greater than 550N, 600N, greater than 650N, or greater than 700N.

[0040] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0041] In another aspect, a battery separator is described herein. The battery separator comprises a microporous film having a resistance value of 2 or less in some embodiments, 1.7 or less in some embodiments, 1.6 or less in some embodiments, 1.5 or less in some embodiments, 1.4 or less in some embodiments, 1.3 or less in some embodiments, 1.2 or less in some embodiments, and 1.0 or less in some embodiments.

[0042] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0043] In another aspect, a battery separator is described comprising a multi-layer microporous film having a mixed permeability value of 380N or more, 400N or more, 450N or more, 500N or more, 550N or more, 600N or more, 650N or more, or 700N or more.

[0044] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0045] In another aspect, a battery separator comprising a multi-layer microporous film having a resistivity of 2.0 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, or 1.0 or less is described.

[0046] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0047] In another aspect, a battery separator comprises a multi-layer microporous film comprising a region comprising two or more layers or microlayers and polyethylene in one or more layers or microlayers. When the region is tested according to the machine learning test described herein, at least one of the following is satisfied: T x'≥-4, W T x'≥-2.654, W T x' ≥ 1.3 and W T x'≥2,WT x' ≥ 2 is most preferred.

[0048] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0049] In another aspect, a battery separator comprises a multi-layer microporous film comprising a region comprising two or more layers or microlayers and polypropylene in one or more layers or microlayers. When the region is tested according to the machine learning test described herein, at least one of the following is satisfied: T x'≥-5, W T x'≥-3, W T x'≥0, W T x'≥≥3,W T x' ≥ 3 is most preferred.

[0050] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0051] In another aspect, a battery separator comprising a multilayer membrane or microporous film has dielectric breakdown uniformity that is superior to typical separators of similar thickness, porosity, and Gurley value.

[0052] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0053] In another aspect, a battery separator is described. The battery separator comprises at least one multilayer microporous membrane or film having at least two regions or sublayers, each region or sublayer comprising at least two micron layers, the multilayer membrane having or exhibiting at least one of the following: (a) a mixed permeability (N) value greater than 380N; (b) a mixed permeability (N) value greater than 600N; (c) a curvature of 1.8 or greater; (d) an average dielectric breakdown value (V) that is 1 to 35% higher than the average dielectric breakdown value of a three-layer microporous film having the same thickness, Gurley value and / or porosity as the multilayer microporous film; (e) a minimum dielectric breakdown value of a three-layer microporous membrane or film having the same thickness, Gurley value and / or porosity as the multilayer microporous membrane that is 3 to 20% higher (f) having dielectric breakdown uniformity; (g) passing a nail penetration test; (h) having at least one micron layer comprising PO, PP and / or PE and an elastomer; (i) having at least one micron layer comprising siloxane; (j) having at least one micron layer comprising PP and an elastomer; (k) having at least one micron layer comprising a copolymer; (l) having at least one micron layer comprising PP and a copolymer; (m) having at least two micron layers comprising different resins or resin blends; (n) when one of the regions comprises polypropylene in one or more micron layers, wherein when this region is tested according to the machine learning test described herein, at least one of the following is satisfied: W T x'≥-5 or W T x'≥-3; (0) when one of the regions comprises polypropylene in one or more micron layers, wherein when this region is tested according to the dimension reduction technique referred to as PCA described herein, at least one of the following is satisfied: W T x' ≥ 0 and W T x'≥3; (p) when one of the regions comprises polyethylene in one or more micron layers, wherein when the region is tested according to the machine learning test described herein, at least one of the following is satisfied: W T x' ≥ -4 and W T x'≥-2.654; (q) when one of the regions comprises polyethylene in one or more micron layers, wherein when this region is tested according to the machine learning test described herein, at least one of the following is satisfied: W T x' ≥ 1.3 and W Tx'≥2; (r) one of the regions comprises PE and, when measured by DSC, has a crystallinity that is 1 to 20% lower than the crystallinity of the PE-containing layer of a three-layer microporous membrane or film having the same thickness, Gurley value and / or porosity as the multi-layer microporous film; (s) the microporous multi-layer membrane or film has 30 to 100 micron layers or more; (t) at least one of the micron layers comprises lithium stearate; (u) the multi-layer microporous film exhibits reduced MD or TD cracking; (v) at least one of the micron layers comprises PE beads; (w) has a needle removal force of less than 50N; (x) exhibits reduced contact with the needle; (y) has reduced MD or TD cracking; (z) can be a precursor to at least one of transverse direction (TD) stretching, calendaring and hole filling. In some embodiments, the microporous multilayer film exhibits one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more, eleven or more, twelve or more, thirteen or more, fourteen or more, fifteen or more, sixteen or more, seventeen or more, eighteen or more, nineteen or more, twenty or more, twenty-one or more, twenty-two or more, twenty-three or more, twenty-four or more, twenty-five or more, or twenty-six of the twenty-six options. The separator may also include other properties. In some embodiments, one or more surfaces of the battery separator are coated. And in some embodiments, it is not coated. In some embodiments, the coating is a ceramic coating.

[0054] In another aspect, described herein is a battery, in particular a lithium ion battery, comprising at least one separator as described in the preceding paragraph.

[0055] On the other hand, a method for forming an improved battery separator comprising a multilayer microporous membrane or film is described herein. The method includes at least the following steps: coextruding at least two layers, and laminating at least two coextruded layers to one other layer, or in some embodiments, laminating to two other layers to form a multilayer microporous membrane. In some embodiments, at least two, three, four, five, six, seven, eight, nine or ten layers are coextruded. In some embodiments, at least one other layer or at least two other layers is a coextruded layer. In some embodiments, at least one other layer is a single extrusion layer. In embodiments where at least two coextruded layers are laminated to two other layers, sometimes, one of the two other layers is laminated to the first side of the at least two coextruded layers, and the second of the two other layers is laminated to the side of the at least two coextruded layers opposite to the first side. At least one of the two other layers can be a coextruded layer. In some embodiments, both other layers are coextruded layers. In some embodiments, at least two coextruded layers and at least one of the other layers contain a polyolefin or a polyolefin blend. For example, it may include polyethylene or polyethylene blends, or polypropylene or polypropylene blends. In some embodiments, at least one of at least two coextruded layers includes polyethylene, and at least one or both of the other layers include polypropylene or polyethylene blends. In some embodiments, at least one of at least two coextruded layers includes polyethylene, and at least one or both of the other layers include polypropylene or polypropylene blends. In some embodiments, each of two other layers includes polyethylene or polyethylene blends. In some embodiments, each of two other layers includes polypropylene or polypropylene blends. In some embodiments, one or both of the other layers are coextruded layers, which are coextruded with 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more or 9 or more other layers. When these layers are coextruded with 9 other layers, the total number of coextruded layers is 10.

[0056] In another aspect, a battery separator is made by the method described in the preceding paragraph.

[0057] Brief description of the accompanying drawings

[0058] Figure 1 2,500 times magnification, is a partial cross-sectional scanning electron micrograph (SEM) of an exemplary laminated three or three groups of three-layer microporous membranes of the present invention, three layers / three layers / three layers (each three-layer layer has 9 coextruded microlayers, and each PP or PE sublayer of each three-layer layer has 3 microlayers).

[0059] Figure 2 yes Figure 1 A local cross-sectional scanning electron micrograph (SEM) of a portion of a polypropylene surface sublayer (3 micro-layers of PP) of the surface three-layer component or sub-layer film of a composite laminated film, at a magnification of 15,000 (the PP sublayer is magnified, it is actually 3 coextruded PP micro-layers, and it is difficult to discern the interface).

[0060] Figure 3 yes Figure 1 Scanning electron micrograph (SEM) of a partial cross section of a polyethylene sublayer (3 micron layer of PE), one of the three 9 micron layers of a 3-layer membrane, at a magnification of 15,000 (the PE sublayer is magnified).

[0061] Figure 4 is a graph showing the improved cycling behavior of an exemplary inventive configuration compared to COM EX 1.

[0062] Figure 5 is a graph showing the compressive elastic results for a specific construction compared to COM EX 1.

[0063] Figure 6 is a graph showing the Hybrid P penetration test results for a specific configuration compared to COM EX 1.

[0064] Figure 7 Schematic diagram of how micron layers are produced at the feed end by adding layers in the coextrusion process.

[0065] Figure 8 Schematic diagram of how micron layers are produced by splitting the layers in the coextrusion process.

[0066] Fig. 9 is a cross-sectional scanning electron micrograph (SEM) of an exemplary 3 or tri-layer (9 micro-layers total, with 3 sets of micro-layer sub-layers laminated together) PP / PE / PP microporous membrane of the present invention, at a magnification of 5,000 times (at least the outer PP sub-layer is microporous).

[0067] Fig.10 yes Fig. 9 Surface scanning electron micrograph (SEM) of the polypropylene surface sublayer (surface PP microlayer) of a 3-layer film having 9 micrometer layers at 3,000 magnifications. This 9 micrometer layer film can be used as Figure 1 One of the 3-layer films (9 sublayers, 27 micron layers) shown.

[0068] Fig.11 yes Fig. 9 Surface scanning electron micrograph (SEM) of a portion of the surface of a polypropylene surface sublayer (surface PP microlayer) of a 3-layer film having 9 micrometer layers, at a magnification of 10,000.

[0069] Fig.12 yes Fig. 9 Surface scanning electron micrograph (SEM) of a portion of the surface of a polypropylene surface sublayer (surface PP microlayer) of a 3-layer film having 9 micrometer layers, at a magnification of 30,000.

[0070] Fig.13 1 is a cross-sectional scanning electron micrograph (SEM) of an exemplary 3 "microlayer" coextruded sublayer (PO1 / PO2 / PO1) microporous membrane of the present invention, at a magnification of 5,000 times (at least the outer PO1 microlayer is microporous), the microlayer PO2 is made of a different resin or resin blend than the microlayer PO1 to more clearly show the interface (interfacial region) of adjacent coextruded microlayers. It is believed that the multiple coextruded microlayer interfaces and the lamination interfaces between adjacent sublayers provide unique characteristics, properties and / or performance for the multilayer structure of the present invention. Fig.13 The example sublayer is made of 3 PP layers, the middle PP layer has a different PP resin from the outer two layers, and due to the lower viscosity of the middle PP layer, a thicker precursor must be used (usually, each micron layer will be less than 4μm, preferably less than 3μm, more preferably less than 2μm).

[0071] Fig.14 yes Fig.13 A portion of the SEM is labeled with red and green horizontal lines showing the interface region.

[0072] Fig.15 yes Fig.13 A magnified image showing the unique pore structure and membrane architecture.

[0073] Fig.16 is a schematic diagram of an exemplary 12 μm three-layer according to at least one embodiment of the present invention (which is PP / PE / PP sublayers or microlayers laminated together, each sublayer is different, the top PP sublayer has 3 coextruded PP microlayers; the middle PE sublayer has 3 PE microlayers, which can be the same or different from each other; the bottom PP sublayer has 2 PP blend microlayers and a PP microlayer). Fig.16 It is shown that in a 9 micro-layer film, there can be many different embodiments, and variations in sub-layers and individual micro-layers are possible and desirable. For example, one may want to add some PE to the outermost PP micro-layer to increase adhesion, wettability, lamination bond strength, and / or the like.

[0074] Fig.17 It is a schematic diagram of an exemplary 3, 9, 18 or 21 micron layer implementation or example according to the present invention (blue represents PP micron layer, yellow represents PE micron layer, and the numbered black lines indicate interfaces). Fig.17It is shown that there can be many different embodiments and variations in the use of PP or PE sublayers are possible and desirable. For example, one may want to add some PE to the outer or middle sublayer to increase adhesion, wettability, lamination bond strength or provide a closure function to the middle and / or the like. Fig.18 Improved DB uniformity data is shown for several examples of multi-layer products (EX 1, EX 3, EX 6) compared to other more conventional three-layer products.

[0075] Fig.18 Improved DB uniformity data is presented for several multi-layer product examples (EX 1, EX 3, EX 6) compared to other more conventional three-layer products.

[0076] Fig.19 is a graph demonstrating the improved cycling behavior of an exemplary inventive construction (EX 1) compared to a conventional 12 μm tri-layer product. The comparative film shown here is a 12 μm tri-layer (PP / PE / PP) (no micron layer). This was performed at a C-rate of C / 3 with a cutoff of 4.3 V in the 523 NCM vs. graphite system. The data shown represents the average of 5 cells per sample (or 10 cells total). Possibly due to the increased electrolyte utilization resulting from the increased complexity of the interface and pore structure, we can see a reproducible improvement in the cycle life of EX 1 over the conventional tri-layer.

[0077] Fig. 20 Various non-limiting exemplary embodiments, features, advantages or configurations of the multi-layered products and concepts of the present invention are listed.

[0078] Fig.21 It is a cross-sectional SEM at 10,000 times, showing a PP / PE / PP sublayer of 9 microlayers (each sublayer has 3 microlayers) of about 14μm film, which has a middle PE sublayer of about 3.11μm thick (each PE microlayer is only about 1.037μm thick each). The present invention can be used to prepare a multi-layer microlayer structure from a polyolefin resin, which has superior performance to other PO films, with each microlayer having a thickness of 2μm or less, each microlayer having a thickness of 1.5μm or less, each microlayer having a thickness of 1.3μm or less, each microlayer having a thickness of 1.15μm or less, each microlayer having a thickness of 1.05μm or less, and / or the like.

[0079] Figure 22 presents data for several multi-layer product embodiments (EX 1, EX 3, EX 2, EX 4, and EX 6) compared to other more conventional three-layer products (COM EX 1, COM EX 3, COM EX 2, COM EX 4). Normalization for thickness and porosity helps to demonstrate some of the advantages of the new multi-layer structure.

[0080] Fig.23 More data is given for several multi-layer product examples (EX 1, EX 3, EX 4, and EX 6) compared to other more conventional three-layer products (COM EX 1, COM EX 3, COM EX 2, COM EX 4). Normalization for thickness and porosity helps to show some of the advantages of the new multi-layer structure. m =T 2 / P calculates the curvature, where N m is the McMillan number, T is the curvature, and P is the porosity.

[0081] Fig.24 SEM image of a polypropylene layer comprising a multilayer product according to some embodiments described herein.

[0082] Fig.25 SEM image of the polypropylene layer comprising a more conventional three-layer product described herein.

[0083] Fig.26 SEM image of a polyethylene layer comprising a multilayer product according to some embodiments described herein.

[0084] Fig. 27 SEM image of the polyethylene layer comprising a more conventional three-layer product described herein.

[0085] Fig.28 Included are SEM images showing a side-by-side comparison of the polypropylene layers of the three-layer and multi-layer products described herein.

[0086] Fig.29 Included are SEM images showing a side-by-side comparison of the polyethylene layers of the three-layer and multi-layer products described herein.

[0087] Fig.30 Included are SEM images showing a side-by-side comparison of the three- or multi-layer products described herein.

[0088] Fig.31 is a table of DSC data for the polyethylene layer of the multi-layer and tri-layer products described herein.

[0089] Fig.32 Table 2 is the DSC data for the polypropylene layer of the multi-layer and tri-layer products described herein.

[0090] Fig.33 is a graph showing a quantitative evaluation of the pore size distribution (using mercury intrusion porosimetry) of the multi-layer and tri-layer products described herein.

[0091] Fig.34 Shown is the normalization of x to x' (in PP) according to the machine learning test described in this paper.

[0092] Fig.35 Coefficients and boundary parameters (PP) based on the machine learning tests described in this paper are shown.

[0093] Fig.36 Shown is the normalization of x to x' (in PE) according to the machine learning test described in this paper.

[0094] Fig.37 Coefficients and boundary parameters (PE) based on the machine learning tests described in this paper are shown.

[0095] Figures 38 to 50 Schematic diagrams of specific coextruded multilayer precursors, films or separators, respectively, according to some additional embodiments described herein. DETAILED DESCRIPTION OF THE INVENTION

[0097] By referring to the following detailed description, examples and figures, the embodiments described herein can be more easily understood. However, the elements, devices and methods described herein are not limited to the specific embodiments presented in the detailed description, examples and figures. It should be appreciated that these embodiments are merely illustrations of the principles of the present invention. It will be apparent to those skilled in the art that various modifications and adjustments will be apparent without departing from the spirit and scope of the present invention.

[0098] In addition, all ranges disclosed herein are to be understood to include any and all subranges contained therein. For example, a stated range of "1.0 to 10.0" should be considered to include any and all subranges starting from a minimum value of 1.0 or higher and ending at a maximum value of 10.0 or lower, such as 1.0 to 5.3 or 4.7 to 10.0 or 3.6 to 7.9.

[0099] Unless otherwise expressly stated, all ranges disclosed herein should also be considered to include the endpoints of the range. For example, a range of "between 5 and 10", "from 5 to 10" or "5-10" should generally be considered to include the endpoints 5 and 10.

[0100] In addition, when the phrase "up to" is used in conjunction with an amount or quantity, it is understood that the amount is at least a detectable amount or quantity. For example, a material present in an amount "up to" a specific amount can be present in amounts from a detectable amount up to and including the specific amount.

[0101] Described herein are: microporous multilayer films or membranes; battery separators comprising at least one microporous multilayer film or membrane; batteries, particularly lithium-ion batteries, comprising at least one battery separator described herein, devices comprising the batteries described herein, and methods of making microporous multilayer films or membranes.

[0102] The multi-layer microporous film or membrane exhibits improved properties, particularly when compared to previous three-layer and multi-layer microporous films having the same thickness, Gurley value and / or porosity, the improved properties of the film or membrane include but are not limited to: improved puncture strength (gf) compared to previous three-layer and multi-layer products, improved mixed permeability average (N) compared to previous three-layer and multi-layer products, improved tensile strength (kgf / cm2) compared to previous three-layer and multi-layer products, and improved tensile strength (kgf / cm2) compared to previous three-layer and multi-layer products. 2 ), faster closing speed (ohm-cm) compared to previous three-layer and multi-layer products 2 ), higher average dielectric breakdown (DB) values ​​(V) compared to previous three-layer and multi-layer products, smaller DB standard deviations (V) compared to previous three-layer and multi-layer products, higher minimum DB values ​​(V) compared to previous three-layer and multi-layer products, passing industrial nail penetration tests that previous three-layer and multi-layer microporous films could not pass, and improved cycle life compared to previous three-layer and multi-layer products. It was also found that the multi-layer microporous films herein have a unique structure. The unique structure of these films explains many of the observed improved properties.

[0103] Battery separator

[0104] The battery separators herein comprise, consist of, or consist essentially of (i.e., one or more) a multilayer film or a multilayer microporous film, and optionally have a coating on one or both sides of the film. The film itself, i.e., without the coating or any other additional components, exhibits the improved properties described above. The properties of the film can be enhanced by adding a coating or other additional components.

[0105] (1) Multi-layer microporous film or membrane

[0106] In some embodiments, the multilayer membrane or multilayer microporous film comprises 4 or more layers, 5 or more layers, 6 or more layers, 7 or more layers, 8 or more layers, 9 or more layers, 11 or more layers, 12 or more layers, 13 or more layers, 14 or more layers, 15 or more layers, 15 or more layers, 16 or more layers, 17 or more layers, 18 or more layers, 19 or more layers, 20 or more layers, 21 or more layers, 22 or more layers, 23 or more layers, 24 or more layers, 25 or more layers, 26 or more layers, 27 or more layers, 28 or more layers, 29 or more layers, 30 or more layers, 40 or more layers, 50 or more layers, 60 or more layers, 70 or more layers, 80 or more layers, 90 or more layers, or 100 or more layers. The term "layer" includes a single extruded layer having a thickness of 2 to 20 microns. As understood by those skilled in the art, a single extruded layer is a layer extruded by itself without any other layers. Moreover, in determining whether a given battery separator is a multi-layer battery separator, each of the layers in a coextruded two-layer, three-layer or multi-layer film is considered a "layer". The number of layers in a coextruded two-layer is two, the number of layers in a coextruded three-layer is three, and the number of layers in a coextruded multi-layer film is two or more, preferably three or more. The exact number of layers in a two-layer, three-layer or multi-layer coextruded film is determined by the die design and not by the material that is coextruded to form the coextruded film. For example, a coextruded two-layer, three-layer or multi-layer film can be formed by using the same material to form each of the two, three or four or more layers; and even if each layer is made of the same material, the layers will still be considered separate layers. The exact number will again be determined by the die design. Each layer of the coextruded two-layer, three-layer or multilayer film has a thickness of 0.01 to 20 microns, preferably 0.1 to 5 microns, most preferably 0.1 to 3 microns, 0.1 to 2 microns, 0.1 to 1 micron, 0.01 to 0.9 microns, 0.01 to 0.8 microns, 0.01 to 0.7 microns, 0.01 to 0.6 microns, 0.01 to 0.5 microns, 0.01 to 0.4 microns, 0.01 to 0.3 microns or 0.01 to 0.2 microns. These layers are micron layers.

[0107] In some embodiments, the multilayer microporous film or multilayer microporous membrane disclosed herein comprises two or more, or preferably three or more coextruded layers. A coextruded layer is a layer formed by a coextrusion process. At least two or preferably at least three continuous coextruded layers can be formed by the same or independent coextrusion process. For example, at least two or at least three continuous layers can be formed by the same coextrusion process; or two or more layers can be coextruded by a process, two or more layers can be coextruded by an independent process, and two or more layers formed by a process can be laminated with two or more layers formed by an independent process to combine them into four or more continuous coextruded layers. In some preferred embodiments, two or more, or preferably three or more coextruded layers are formed by the same coextrusion process. For example, two or more, or preferably three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, ten or more, fifteen or more, twenty or more, twenty-five or more, thirty or more, thirty-five or more, forty or more, forty-five or more, fifty or more, fifty-five or more or sixty or more coextruded layers may be formed by the same coextrusion process. In a further preferred embodiment, the extrusion process is carried out by extruding a mixture of two or more polymers, which may be the same or different, in the absence of a solvent. A preferred coextrusion process is a dry process, for example Dry process.

[0108] In some embodiments, the multilayer microporous film or multilayer film described herein is prepared by forming a coextruded two-layer (two coextruded layers), three-layer (three coextruded layers) or multilayer (two or more, preferably three or more coextruded layers) film and then laminating the two-layer, three-layer or multilayer film to at least one (but preferably two) other films. At least one (but preferably two) other films can be a nonwoven film, a single extruded film or a coextruded film. In a preferred embodiment, the other film is a coextruded film having the same number of coextruded layers as the coextruded two-layer, three-layer or multilayer film. For example, if a coextruded three-layer film is formed, the other layer is also a coextruded three-layer.

[0109] The two, three or more coextruded films may be laminated together with at least one other single extruded monolayer film or two, three or more films using heat, pressure or preferably heat and pressure.

[0110] The polymers or copolymers useful in the battery separator of the present invention are those polymers or copolymers which are extrudable. Such polymers are generally referred to as thermoplastic polymers.

[0111] In some embodiments, one or more layers of the multi-layer microporous film or multilayer membrane comprise polymer or copolymer or polymer or copolymer blend, preferably polyolefin or polyolefin blend. As understood by those of ordinary skill in the art, polyolefin blends may include a mixture of two or more different types of polyolefins (e.g., polyethylene and polypropylene), a blend of two or more polyolefins of the same type, wherein each polyolefin has different properties, e.g., high or ultrahigh molecular weight polyolefin and low or ultralow molecular weight polyolefin, or a mixture of polyolefin and other types of polymers or copolymers or any additives.

[0112] Polyolefins include, but are not limited to, polyethylene, polypropylene, polybutylene, polymethylpentene, copolymers thereof, and blends thereof. In some embodiments, polyolefins may be ultra-low molecular weight, low molecular weight, medium molecular weight, high molecular weight, or ultra-high molecular weight polyolefins, such as medium or high molecular weight polyethylene (PE) or polypropylene (PP). For example, ultra-high molecular weight polyolefins having molecular weights of 450,000 (450k) or more, such as 500k or more, 650k or more, 700k or more, 800k or more, 1 million or more, 2 million or more, 3 million or more, 4 million or more, 5 million or more, 6 million or more may be provided. High molecular weight polyolefins having molecular weights in the range of 250k to 450k, such as 250k to 400k, 250k to 350k, or 250k to 300k may be provided. The medium molecular weight polyolefin having a molecular weight of from 150 to 250k, for example, 100k, 125k, 130k, 140k, 150k to 225k, 150k to 200k, 150k to 200k, etc. can be used. Low molecular weight polyolefins having a molecular weight in the range of 100k to 150k, for example, 100k to 125k can be used. Ultra-low molecular weight polyolefins having a molecular weight less than 100k can be used. The above values ​​are weight average molecular weights. In some embodiments, the strength or other properties of a microporous multilayer film or a battery comprising a microporous multilayer film as described herein can be improved with a higher molecular weight polyolefin. In some embodiments, a polymer of a lower molecular weight, such as a medium, low or ultra-low molecular weight polymer may be advantageous. For example, without wishing to be bound by any particular theory, it is believed that the crystallization behavior of a lower molecular weight polyolefin can produce a microporous multilayer film having smaller pores, the pores being produced by at least the MD stretching process that forms the pores.

[0113] In addition to polyolefin polymers, blends or mixtures, exemplary thermoplastic polymers, blends, mixtures or copolymers may include, but are not limited to: polyacetal (or polyoxymethylene), polyamide, polyester, polysulfide, polyvinyl alcohol, polyvinyl ester and polyvinylidene fluoride (and may include PVDF, PVDF: HFP, PTFE, PEO, PVA, PAN or the like). Polyamides (nylons) include, but are not limited to: polyamide 6, polyamide 66, nylon 10,10, polyphthalamide (PPA), copolymers thereof and blends thereof. Polyesters include, but are not limited to: polyterephthalate, polybutylene terephthalate, copolymers thereof and blends thereof. Polysulfides include, but are not limited to, polyphenylene sulfide, copolymers thereof and blends thereof. Polyvinyl alcohol includes, but is not limited to: ethylene-vinyl alcohol, copolymers thereof and blends thereof. Polyvinyl esters include, but are not limited to, polyvinyl acetate, ethylene vinyl acetate, copolymers thereof and blends thereof. Polyvinylidene fluoride includes, but is not limited to, fluorinated polyvinylidene fluoride (e.g., polyvinylidene chloride, polyvinylidene fluoride), copolymers thereof, and blends thereof. Various materials may be added to the polymer. These materials are added to change or enhance the performance or properties of a single layer or the entire separator. These materials include, but are not limited to, materials that may be added to reduce the melting temperature of the polymer. Typically, a multilayer separator includes a layer designed to close its pores at a predetermined temperature to block the flow of ions between the battery electrodes. This feature is often referred to as shutdown.

[0114] In some embodiments, each layer of the multilayer microporous film or multilayer membrane comprises a different polymer or copolymer or polymer or copolymer blend, or consists of or is substantially composed of a different polymer or copolymer or polymer or copolymer blend. In some embodiments, each layer comprises the same polymer or copolymer or polymer or copolymer blend, or consists of or is substantially composed of the same polymer or copolymer or polymer or copolymer blend. In some embodiments, the alternating layers of the multilayer microporous film or multilayer membrane comprise the same polymer or copolymer or polymer or copolymer blend, or consist of or is substantially composed of the same polymer or copolymer or polymer or copolymer blend. In other embodiments, some layers of the multilayer membrane or microporous multilayer film comprise the same polymer or polymer blend, or consist of or is substantially composed of the same polymer or polymer blend, while some layers do not.

[0115] Although it may be preferred that each layer or microlayer contains a polyolefin (PO) blend, mixture, copolymer, etc., such as PP or PE or PE+PP, or consists of or consists essentially of a polyolefin (PO) blend, mixture, copolymer, etc., such as PP or PE or PE+PP, it is contemplated that other polymers (PY), additives, agents, materials, fillers and / or particles (M) and / or the like may be added or used, and layers or microlayers such as PP+PY, PE+PY, PP+M, PE+M, PP+PE+PY, PE+PP+M, PP+PY+M, PE+PY+M, PP+PE+PY+M or blends, mixtures, copolymers and / or the like may be formed.

[0116] Moreover, the same, similar, different or different PP or PE or PE+PP polymers, homopolymers, copolymers, molecular weights, blends, mixtures, copolymers or the like can be used. For example, the same, similar, different or different molecular weight PP, PE and / or PP+PE polymers, homopolymers, copolymers, multipolymers, blends, mixtures and / or the like can be used in each layer. Thus, the construction can include various combinations and sub-combinations of PP, PE, PP+PE, PP1, PP2, PP3, PE1.PE2, PE3, PP1+PP2, PE1+PE2, PP1+PP2+PP3, PE1+PE2+PE3, PP1+PP2+PE, PP+PE1+PE2, PP1 / PP2, PP1 / PP2 / PP1, PE1 / PE2, PE1 / PE2 / PP1, PE1 / PE2 / PE3, PP1+PE / PP2 or other combinations or constructions.

[0117] In some embodiments, one or more additives may be added to the outermost layer of the multi-layer microporous film or multi-layer membrane to improve its performance or the performance of the battery separator or battery containing it. In addition to the additives, the outermost layer may contain PE, PP or PE+PP. For example, in order to improve needle removal (i.e., reduce the friction coefficient of the film or membrane), additives such as lithium stearate, calcium stearate, PE beads, siloxanes and polysiloxanes may be added.

[0118] In addition, a specific polymer, copolymer or polymer or copolymer blend is used in the outermost layer of the multi-layer microporous film or multi-layer membrane to improve its performance or the performance of the battery separator or battery containing it. For example, adding an ultra-high molecular weight polymer or copolymer in the outermost layer can improve the puncture strength.

[0119] In a further embodiment, an additive to improve oxidation resistance may be added to the outermost layer of the multi-layer microporous film or membrane. The additive may be an organic or inorganic additive or a polymeric or non-polymeric additive.

[0120] In some embodiments, the outermost layer of a multilayer film or membrane can comprise, consist of, or consist essentially of polyethylene, polypropylene, or mixtures thereof.

[0121] In some embodiments, the microporous multilayer film or membrane may comprise three or more different regions or sub-layer film regions. In a preferred embodiment, one or more of the regions or sub-layer film regions may comprise two or more layers, or consist of or consist essentially of two or more layers, which may or may not be coextruded layers. In some preferred embodiments, the two or more layers are coextruded layers. In some embodiments, there is a lamination barrier between a region or sub-layer film region and an adjacent region or sub-layer film region. A lamination barrier is formed when two surfaces (e.g., two surfaces of different films or layers) are laminated together using heat, pressure, but preferably heat and pressure. In some embodiments, the sublayer film region has the following non-limiting structures: PP, PE, PP / PP, PP / PE, PE / PP, PE / PE, PP / PP / PP, PP / PP / PE, PP / PE / PE, PP / PE / PP, PE / PE / PP, PE / PE / PP, PP / PP / PP / PP, PE / PE / PE / PP, PE / PE / PP / PP, PE / PE / PP / PP, PE / PE / PP / PP, PP / PE / PE / PP, PE / PE / PP / PP, PP / PE E / PE / PE / PP, PE / PP / PP / PP / PE, PP / PP / PE / PP / PP, PE / PE / PP / PP / PE / PE, PP / PE / PP / PE / PP, PP / PP / PE / PE / PP / PP, P E / PE / PP / PP / PE / PE, PE / PP / PE / PP / PE / PP, PP / PE / PP / PE / PP / PE, PP / PP / PP / PE / PP / PP / PP, PE / PE / PE / PP / PE / PE / P E. PP / PE / PP / PE / PP / PE / PP, PE / PP / PE / PP / PE / PP / PE, PE / PP / PE / PP / PE / PP / PE / PP, PP / PE / PP / PE / PP / PE / PP / PE, P P / PP / PE / PE / PP / PP / PE / PE, PP / PE / PE / PE / PE / PE / PE / PP, PE / PP / PP / PP / PP / PP / PP / PE, PP / PP / PE / PE / PEPE / PP / PP , PP / PP / PP / PP / PE / PE / PE / PE, PP / PP / PP / PP / PE / PP / PP / PP / PP, PE / PE / PE / PE / PP / PE / PE / PE / PE, PP / PE / PP / PE / PP / PE / PP / PE / PP、PE / PP / PE / PP / PE / PP / PE / PP / PE、PE / PE / PE / PE / PE / PP / PP / PP / PP、PP / PP / PP / PP / PP / PE / PE / PE / PE、PE herein refers to a layer or microlayer of a film region or sublayer comprising, consisting of or consisting essentially of PE, or consisting of PE. PP herein means a layer or micro-layer of a region or sub-layer film region containing PP or consisting of or substantially consisting of PP, such as a coextruded layer or micro-layer. The PE or PP of different layers or micro-layers may be the same or different. Similar variations including up to 50 layers or micro-layers (especially coextruded layers or micro-layers) per region or sub-layer film region may be formed with an appropriate extrusion die.

[0122] In a preferred embodiment, the coextrusion precursor may have a structure such as (PP1 / PP2 / PP3), (PP3 / PP2 / PP1), (PP3 / PP3 / PP2 / PP1 / PP1), (PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP2 / PP1 / PP1 / PP1). PP1 is made of homopolymer PP and additives to change the surface friction coefficient, including any anti-slip or anti-stick additives such as polysiloxanes or siloxanes. PP2 can be made of PP homopolymers and copolymers that are the same or different from PP1. The PP copolymer can be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 can be made of PP homopolymers that are the same or different from PP1 and PP2, and also include additives to change the surface friction coefficient, and the additives can be the same or different from those used in PP1.

[0123] In other preferred embodiments, the coextrusion precursor may have a structure of (PP1 / PP2 / PP3), (PP3 / PP2 / PP1), (PP3 / PP3 / PP2 / PP1 / PP1), (PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP2 / PP1 / PP1 / PP1), etc. PP1 can be any polypropylene blend. PP2 can be made of any PP block copolymer, including those described herein. PP3 can be made of a PP block copolymer that is the same or different from the PP block copolymer used in PP2.

[0124] The regions or sub-layer membrane regions may be arranged in any order to form a microporous multilayer membrane or microporous multilayer film.For example, the microporous multilayer film or microporous multilayer thin film may have the following non-limiting structures: (PP / PP)(PE / PE) / (PP / PP); (PE / PE)(PP / PP)(PE / PE); (PP / PE)(PP / PE)(PP / PE); (PP / PE)(PE / PP)(PE / PP); (PP / PP / PP)(PE / PE / PE)(PP / PP / PP); (PE / PE / PE)(PP / PP / PP)(PE / PE / PE); (PP / PE / PP)(PE / PP / PE)(PP / PE / PP); (PP / PP / PE)(PE / PE / PE)(PE / PP / PP); (PE / PE / PP)(PP / PP / PP)(PP / PE / PE); (PE / PP / PE) / (PP / PE / PP)(PE / PP / PE); (PP / PE / PP)(PE / PP / PE)(PP / PE / PP); (PP / PE / PP)(PP / PE / PP)(PP / PE / PP); (PP / PP / PP)(PP / PP / PP)(PP / PP / PP); (PE / PE / PE)(PE / PE / PE)(PE / PE / PE); (PE / PE / PE)(PP)(PE / PE / PE); (PP / PP / PP)(PE)(PP / PP / PP); (PE / PE / PE)(PP / PP)(PE / PE / PE); (PP / PP / PP)(PE / PE)(PP / PP / PP); (PE / PP / PE)(PP)(PE / PP / PE); (PP / PE / PP)(PE)(PP / PE / PP); (PE / PP / PE)(PP / PP)(PE / PP / PE); (PP / PE / PP)(PE / PE)(PP / PE / PP); (PP / PP / PP / PP)(PE)(PP / PP / PP / PP); (PE / PE / PE / PE)(PP)(PE / PE / PE / PE); (PP / PP / PP / PP / PP)(PE)(PP / PP / PP / PP / PP); (PE / PE / PE / PE / PE)(PP / PP)(PE / PE / PE / PE / PE); (PP / PP / PP / PP / PP)(PE / PE / PE / PE / PE)(PP / PP / PP / PP / PP); (PE / PE / PE / PE / PE / PE)(PP / PP / PP / PP / PP)(PE / PE / PE / PE / PE); (PP / PE / PP / PE / PP)(PE / PP / PE / PP / PE)(PP / PE / PP / PE / PP); (PE / PP / PE / PP / PE)(PP / PE / PP / PE / PP)(PE / PP / PE / PP / PE).The foregoing variations can be used to form microporous multilayer films or membranes having up to 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 layers or microlayers.

[0125] The thickness of the microporous multilayer film or membrane is not limited, but is preferably less than 50 microns, less than 40 microns, less than 30 microns, less than 25 microns, less than 20 microns, less than 19 microns, less than 18 microns, less than 17 microns, less than 16 microns, less than 15 microns, less than 14 microns, less than 13 microns, less than 12 microns, less than 11 microns, less than 10 microns, less than 9 microns, less than 8 microns, less than 7 microns, less than 6 microns, or less than 5 microns. This is the thickness of the multilayer film or membrane before any coating or treatment is applied thereto.

[0126] As used herein, microporous refers to a film, membrane or coating having an average pore size of 2 micrometers or less, preferably 1 micrometer or less, 0.9 micrometer or less, 0.8 micrometer or less, 0.7 micrometer or less, 0.6 micrometer or less, 0.5 micrometer or less, 0.4 micrometer or less, 0.3 micrometer or less, 0.2 micrometer or less, and preferably 0.1 micrometer or less, 0.09 micrometer or less, 0.08 micrometer or less, 0.07 micrometer or less, 0.06 micrometer or less, 0.05 micrometer or less, 0.04 micrometer or less, 0.03 micrometer or less, 0.02 micrometer or less or 0.01 micrometer or less. In a preferred embodiment, the microporous film can be formed by, for example, applying a stretching process (e.g., as in The holes are formed by a dry process.

[0127] In some preferred embodiments, wherein the multi-layer microporous film or membrane is microporous and comprises a sub-membrane or region, the sub-membrane or region comprises PE, or consists of or consists essentially of PE, the multi-layer microporous film or membrane has an average pore size between 0.03 and 0.1, preferably between 0.05 and 0.09, between 0.05 and 0.08, between 0.05 and 0.07 or between 0.05 and 0.06.

[0128] In other preferred embodiments, wherein the multi-layer microporous film or membrane is microporous and comprises sub-films or regions, the sub-films or regions comprise PP, or consist of or consist essentially of PP, the multi-layer microporous film or membrane has an average pore size between 0.02 and 0.06, preferably between 0.03 and 0.05, and more preferably between 0.04 and 0.05 or 0.03 and 0.04.

[0129] In some other preferred embodiments in which the multilayer microporous film or membrane comprises a sub-membrane or region comprising, or consisting of, or consisting essentially of, PP and a sub-membrane or region comprising, or consisting of, or consisting essentially of PE, the average pore size of the PP sub-membrane or region is smaller than the average pore size of the PE sub-membrane or region.

[0130] There is no limitation on the Gurley value of the microporous multilayer film or membrane, and the film or membrane may have any Gurley value that makes it suitable for use as a battery separator. In some embodiments, the microporous multilayer film or membrane described herein has a JIS Gurley value of 150 (s / 100cc) or greater, 160 or greater, 170 or greater, 180 or greater, 190 or greater, 200 or greater, 210 or greater, 220 or greater, 230 or greater, 240 or greater, 250 or greater, 260 or greater, 270 or greater, 280 or greater, 290 or greater, 300 or greater, 310 or greater, 320 or greater, 330 or greater, 340 or greater, or 350 or greater.

[0131] There is no limit to the porosity of the microporous multilayer film. For example, any porosity that can form an acceptable battery separator is acceptable. In some embodiments, the porosity of the film or membrane can be 10 to 60%, 20 to 60%, 30 to 60%, or 40 to 60%.

[0132] The microporous multilayer film or membrane can have a puncture strength of 290 gf or more, 300 gf or more, 310 gf or more, 320 gf or more, 330 gf or more, 340 gf or more, 350 gf or more, or up to 400 gf or more when uncoated.

[0133] The microporous multilayer film or membrane may have any average dielectric breakdown that is not inconsistent with the objectives described herein. In some embodiments, the average dielectric breakdown value is better than or higher than the average dielectric breakdown value of a three-layer microporous film having at least one of the same thickness, Gurley value, and porosity. For example, it may be 1 to 35% higher, 5 to 35% higher, 10 to 35% higher, 15 to 35% higher, 20 to 35% higher, 25 to 35% higher, or 30 to 35% higher than the average dielectric breakdown value of a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

[0134] There is no limit to the minimum dielectric breakdown value of the microporous multilayer film or membrane. In some embodiments, the minimum value may be better than or higher than the minimum value of a three-layer microporous film with the same thickness, Gurley value and / or porosity. For example, the minimum dielectric breakdown value may be 3 to 20% higher, 5 to 15% higher, 10 to 15% higher, 5 to 10% higher, 3 to 10% higher, 3 to 15% higher, 15 to 20% higher, 10 to 20% higher, or 5 to 20% higher than the minimum dielectric breakdown value of a three-layer microporous film with the same thickness, Gurley value and / or porosity.

[0135] There is also no limit to the standard deviation of the dielectric breakdown value. In some embodiments, it is better than (i.e., lower than) a three-layer microporous film with the same thickness, Gurley value and / or porosity. For example, the standard deviation can be 10 to 55% lower, 10 to 50% lower, 10 to 45% lower, 10 to 40% lower, 10 to 35% lower, 10 to 30% lower, 10 to 25% lower, 10 to 20% lower, or 10 to 15% lower.

[0136] Higher average and minimum DB values ​​and lower DB standard deviations indicate a film that can be used to provide safer battery separators and batteries. Dielectric breakdown is the voltage value at which current begins to flow through an insulator. Higher values ​​obviously indicate a separator that can withstand higher voltages. Higher minimum values ​​are also important because a battery separator is only as safe as its weakest point. Even if the average is high, it is not good if the point at which the film breaks down is at a lower value. The lower DB value standard deviations for the multi-layer microporous films described herein show the consistency of the microporous multi-layer films described herein in terms of safety.

[0137] There is also no limitation on the average (N) of the mixed permeability of the microporous multilayer films or membranes described herein. For example, the mixed permeability value can be 380N or more, 390N or more, 400N or more, 410N or more, 420N or more, 440N or more, 450N or more, 460N or more, 470N or more, 480N or more, 500N or more, 510N or more, 520N or more, 550N or more, 560N or more, 580N or more, 600N or more, 620N or more, 640N or more, 660N or more, 680N or more, 690N or more, 700N or more, 710N or more, 720N or more, 740N or more, 750N or more, 760N or more.

[0138] There is no limitation on the MD shrinkage of the multi-layer microporous film or membrane described herein, but it is preferably lower than the MD shrinkage of the existing three-layer microporous film. For example, the MD shrinkage % at 105° C. is less than 3%, preferably less than 2.5%, more preferably less than 2% or less than 1.5%, and most preferably less than 1%.

[0139] There is no limitation on the MD tensile strength of the microporous multilayer film, but a high MD tensile strength is preferred. For example, it is higher than 1800 kgf / cm 2 , higher than 2000kgf / cm 2 , higher than 2100kgf / cm 2 , higher than 2200kgf / cm 2 , higher than 2250kgf / cm 2 , higher than 2300kgf / cm 2 , higher than 2400kgf / cm 2 Or higher than 2500kgf / cm 2 .

[0140] There is no limit to the MD stretch of the microporous multilayer film. For example, in some embodiments, it is greater than 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60%.

[0141] There is no limitation on the TD tensile strength of the microporous multilayer film. For example, in some embodiments, the TD tensile strength is 120 kgf / cm 2 or above, 125kgf / cm 2 or above, 130kgf / cm 2 or above, 135kgf / cm 2 or above, 140kgf / cm 2 or above, 145kgf / cm 2 or above, 150kgf / cm 2 or above, 155kgf / cm 2 or above, 160kgf / cm 2 or above, 165kgf / cm 2 or above, 170kgf / cm 2 or above, 175kgf / cm 2 or above, 180kgf / cm 2 or above, 185kgf / cm 2 or above, or 190kgf / cm 2 or above, or 195kgf / cm 2 or above.

[0142] There is no limit to the TD stretch of the microporous multilayer film. For example, it can be greater than 500%, greater than 550%, greater than 600%, greater than 650%, greater than 700%, greater than 750%, greater than 800%, greater than 850%, greater than 900%, greater than 950% or greater than 1000%.

[0143] The shutdown temperature of the microporous multilayer film is not limited, but is preferably 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 170°C or higher, 180°C or higher, 190°C or higher or 200°C or higher.

[0144] There is no limitation on the closing speed of the microporous multilayer film, but it is preferably 6,000 ohm-cm 2 or higher, 7,000ohm-cm 2 or higher, 8,000ohm-cm 2 or higher, 9,000ohm-cm 2 or higher, 10,000ohm-cm 2 or higher, 11,000ohm-cm 2 or higher, 12,000ohm-cm 2 or higher, 13,000ohm-cm 2 or higher, 14,000ohm-cm 2 or higher, 15,000ohm-cm 2 or higher, 16,000ohm-cm 2 or higher, 17,000ohm-cm 2 or higher, 18,000ohm-cm 2 or higher, 19,000ohm-cm 2 or higher, or 20,000ohm-cm 2 or higher.

[0145] A higher shutdown speed also indicates a safer battery separator. The faster a battery can shut down, the better it is at preventing thermal runaway.

[0146] In some embodiments, the microporous multilayer membranes or films described herein can surprisingly exhibit improved strength properties, as defined by reduced cracking or reduced tendency to crack, when compared to known battery separators of the same (or greater) thickness, particularly compared to known dry process battery separators of the same (or greater) thickness. The improvement in cracking or cracking can be quantified as a composite cracking index (CSI) by the test methods disclosed herein, and new or improved separators formed from the membranes or films described herein can have improvements in CSI.

[0147] With respect to the structural features of the microporous multilayer films and membranes described herein, in some embodiments, the curvature of the film is greater than 1.6, greater than 1.7, greater than 1.8, greater than 1.9, greater than 2.0, greater than 2.1, or greater than 2.2. Without wishing to be bound by any particular theory, it is believed that the observed curvature values, particularly values ​​greater than 2.0, 2.1, or 2.2, may be responsible for the improved puncture strength and hybrid permeation averages disclosed herein. It is also believed that more curved films are safer when used as battery separators for lithium-ion batteries.

[0148] The microporous multilayer films or membranes described herein have a McMillan number greater than 5.0, greater than 5.5, greater than 6.0, greater than 6.5, greater than 7.0, greater than 7.5, greater than 8.0, greater than 8.5, greater than 9.0, greater than 9.5, greater than 10.0 or greater than 10.5.

[0149] In some embodiments, the microporous multilayer film or membrane has an electrical resistance greater than 0.9, greater than 1.0, greater than 1.1, greater than 1.2, greater than 1.3, greater than 1.4, greater than 1.5, greater than 1.6, or greater than 1.7.

[0150] The crystallinity of the microporous multilayer films described herein is found to be different from the crystallinity of existing multilayer and trilayer films. For example, in some embodiments wherein the microporous multilayer film comprises: (1) a first region comprising two or more layers; (2) a second region comprising two or more layers located on a first side of the first region; and (3) a third region comprising two or more layers located on a side opposite to the first side of the first region; at least one of the first, second, or third regions comprises PE and has a lower crystallinity than the PE-containing layer of the trilayer microporous film when measured by DSC, wherein the trilayer microporous film has the same thickness as the multilayer microporous film. For example, the crystallinity can be 1 to 20%, 1 to 19%, 1 to 18%, 1 to 17%, 1 to 16%, 1 to 15%, 1 to 14%, 1 to 13%, 1 to 12%, 1 to 11%, 1 to 10%, 1 to 9%, 1 to 8%, 1 to 7%, 1 to 6%, 1 to 5%, 1 to 4%, 1 to 3%, or 1 to 2% lower than the PE-containing layer of a three-layer microporous film (wherein the three-layer microporous film has the same thickness as the multi-layer microporous film).

[0151] Another structural difference between the multilayer microporous films described herein and prior art three-layer and multilayer films can be observed using scanning electron microscopy. Figure 25-31 As shown in the figure, for example, Figure 25-31In the invention, the multilayer microporous film or membrane may comprise at least a first region (which comprises two or more layers) and a second layer (which comprises at least one layer). When observed in the z direction of the film with a SEM, the first region may mainly comprise a non-continuous amorphous region. The term "mainly" means that most but not necessarily all of the amorphous regions in the first layer are non-continuous. This may mean that at least 50%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 95%, more than 99% or 100% of the amorphous regions in the first layer are continuous. "Non-continuous amorphous regions" means that when a sample of the first layer is analyzed, for example, by SEM, the path of the amorphous region is interrupted or destroyed by the crystalline (lamellae) region along the total thickness direction of the first layer. Non-continuous means that the path of the amorphous region is interrupted or destroyed by the crystalline (lamellae) region along the total thickness direction of the first layer. The path of the amorphous region does not surround the crystalline (lamellae) region. In contrast, the crystalline (lamellae) regions completely disrupt the path of the amorphous regions through the total thickness of the first layer. The path of the amorphous regions can be linear or tortuous. Fig.29 An example of the difference between discontinuous amorphous regions and continuous amorphous regions can be seen by comparing the SEM of a polyethylene layer of COMEX4 and the SEM of a polyethylene layer of RO397. Discontinuous also means that the amorphous region is non-columnar, non-vertically continuous, or not columnar through the thickness of the layer. In some preferred embodiments, the first region of predominantly discontinuous amorphous regions may comprise, consist of, or consist essentially of polypropylene in some or all of the layers in that region. In some other embodiments, the second region comprises two or more layers and the amorphous region in that region of the film or membrane has a maximum width of 0.85 microns, 0.8 microns, 0.75 microns, 0.70 microns, 0.65 microns, or 0.6 microns. For example, in Fig.30 This can be seen in COM EX 4 compared to R037. In some preferred embodiments, the second region may comprise, consist of or consist essentially of polyethylene in some or all of the layers in that region.

[0152] (2) Optional coating

[0153] In some embodiments, one or more coating layers may be applied to one or both sides of a microporous membrane or film to form a battery separator. In some embodiments, one or more of the coatings may be a ceramic coating comprising a polymer binder and organic and / or inorganic particles, or consisting of or substantially consisting of a polymer binder and organic and / or inorganic particles. In some embodiments, the ceramic coating is applied only to one or both sides of the microporous membrane or film. In other embodiments, different coatings may be applied to the microporous membrane or film before or after the ceramic coating is applied. Different additional coatings may also be applied to one or both sides of the membrane or film. In some embodiments, different polymer coating layers may comprise at least one of polyvinylidene fluoride (PVdF) or polycarbonate (PC), or consist of or substantially consist of at least one of polyvinylidene fluoride (PVdF) or polycarbonate (PC).

[0154] In some embodiments, the coating layer has a thickness of less than about 12 μm, sometimes less than 10 μm, sometimes less than 9 μm, sometimes less than 8 μm, sometimes less than 7 μm, and sometimes less than 5 μm. In at least certain selected embodiments, the coating layer is less than 4 μm, less than 2 μm, or less than 1 μm.

[0155] There is no limitation on the coating method, and the coating layer described herein can be coated on the porous substrate by at least one of the following coating methods: extrusion coating, roll coating, gravure coating, printing, blade coating, air knife coating, spray coating, dip coating or curtain coating. The coating process can be carried out at room temperature or at an elevated temperature.

[0156] The coating layer may be any of nonporous, nanoporous, microporous, mesoporous or macroporous. The coating layer may have a JIS Gurley value of 700 or less, sometimes 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0157] One or more layers, treatments, materials or coatings (CT) and / or webs, meshes, mats, wovens or nonwovens (NW) may be added on one or both sides or within the multilayer films or membranes (M) described herein, which may include but are not limited to CT / M, CT / M / CT, NW / M, NW / M / NW, CT / M / NW, CT / NW / M / NW / CT, CT / M / NW / CT, etc.

[0158] method

[0159] There is no limitation on the method used to form the multi-layer microporous film or membrane described herein, which can be a dry process, preferably Dry stretching processes, such as BNOPP, or wet processes using solvents or oils.

[0160] The method for forming the multilayer microporous film or membrane described herein comprises at least the following steps: (1) coextruding two or more polymer mixtures, which may be the same or different, to form a coextruded film having two or more layers or microlayers as described above; (2) laminating the coextruded film to at least one other monoextruded film, coextruded film or nonwoven. In some preferred embodiments, the coextruded film is laminated to two other coextruded films having two or more microlayers; and (3) optionally one or more additional steps.

[0161] (1) Coextrusion step

[0162] There are no restrictions on coextrusion. Figure 7 An exemplary coextrusion process is given, and Figure 8 A coextrusion die is provided. In some embodiments, coextrusion is performed using a coextrusion die having one or more extruders feeding the die. Typically, there is one extruder for each desired layer or microlayer of the coextruded film that is ultimately formed. For example, if the desired coextruded film has three microlayers, three extruders are used with the coextrusion die. In at least one embodiment, the invented film can be composed of many microlayers or nanolayers, wherein the final product can contain 50 or more layers of individual microlayers or nanolayers. In at least a specific embodiment, the microlayer or nanolayer technology can be produced by a pre-encapsulated feed block before entering a cast film or blown film die.

[0163] In some preferred embodiments, the coextrusion is a bubble coextrusion process, and the blow ratio can vary between 0.5 and 2.0, preferably 0.7 and 1.8, and most preferably 0.9 and 1.5. After coextrusion using this blow ratio, the film can be stretched in MD, stretched in MD and then stretched in TD (with or without MD relaxation), or stretched in MD and TD simultaneously. The film can then be optionally calendered to further control the porosity.

[0164] The benefits of coextrusion include, but are not limited to, increasing the number of layers (interfaces), which, without wishing to be bound by any particular theory, is believed to improve puncture strength. Moreover, without wishing to be bound by any particular theory, coextrusion is believed to have brought about the observed DB improvement. Specifically, the DB improvement may be related to the observed PP pore size reduction when using the coextrusion process. Moreover, by incorporating the blend in the micron layer, coextrusion allows a greater number of material choices. Coextrusion also allows the formation of thin three-layer or multilayer films (coextruded films). For example, a three-layer coextruded film with a thickness of 8 or 10 microns or less can be formed. For higher MD stretch rates, coextrusion allows different pore structures (PP is smaller, PE is larger). Coextrusion can be combined with lamination to produce the desired invented multilayer structure. For example, the structure formed in the embodiment.

[0165] The minimum thickness that can be achieved depends on the extrusion process. In some embodiments, the thinnest PP micron layer can be about 0.19 mil (about 4.83 μm sublayer), while PE is about 0.17 mil (about 4.32 μm sublayer). Each of the 3 micron layers of PP and PE is 0.19 mil and 0.17 mil respectively. For a specific example of a 21-layer structure, for a total extrusion thickness of 1.31 mil (33 μm), we can have about 1.14 mil (or 0.57 mil per side) of PP and 0.17 mil of PE. Using this configuration, we can make a 21-layer product that is only 30 μm or thinner. (2)

[0167] Lamination is not limited and includes placing one surface of the coextruded film and one surface of at least one other film together and fixing the two surfaces to each other using heat, pressure, and / or heat and pressure. For example, heat can be used to increase the tack of either or both surfaces of the coextruded film and at least one other film to make lamination easier, thereby making the two surfaces better adhere or bond together.

[0168] In some preferred embodiments, the laminate formed by laminating the coextruded film to at least one other film is a precursor to a subsequent MD and / or TD stretching step (with or without relaxation).In some embodiments, the coextruded film is stretched prior to lamination.

[0169] (3) Additional Steps

[0170] The additional step may include, consist of, or consist essentially of, MD, TD, or sequential or simultaneous MD and TD stretching steps. The stretching step may be performed before or after the lamination step. Stretching may be performed with or without MD and / or TD relaxation. Co-pending, commonly owned U.S. Patent Application Publication No. US2017 / 0084898A1, published on March 23, 2017, is hereby incorporated by reference in its entirety.

[0171] Other additional steps may include calendering. For example, in some embodiments, the calendering step may be used as a means to reduce the thickness of the porous biaxially stretched film precursor, as a means to reduce its pore size and / or porosity and / or further improve its transverse (TD) tensile strength and / or puncture strength. Calendering can also improve strength, wettability and / or uniformity and reduce surface layer defects introduced in the manufacturing process (e.g., in MD and TD stretching processes). Calendered films or membranes may have improved coating capabilities (using one or more smooth calendering rollers). In addition, using textured calendering rollers helps to improve the adhesion of the coating to the film or membrane.

[0172] The calendering may be cold (below room temperature), ambient temperature (room temperature), or hot (e.g., 90° C.), and may include the application of pressure or the application of heat and pressure to reduce the thickness of the film or film in a controlled manner. The calendering may be in one or more steps, for example, low pressure calendering followed by higher pressure calendering; cold calendering followed by hot calendering, and / or the like. In addition, the calendering process may use at least one of heat, pressure, and speed to densify the heat-sensitive material. In addition, the calendering process may use uniform or non-uniform heat, pressure, and / or speed to selectively densify the heat-sensitive material to provide uniform or non-uniform calendering conditions (e.g., by using smooth rolls, rough rolls, patterned rolls, micro-patterned rolls, nano-patterned rolls, speed changes, temperature changes, pressure changes, humidity changes, dual roll steps, multiple roll steps, or combinations thereof) to produce improved, desired, or unique structures, features, and / or properties to produce or control the resulting structures, features, and / or properties, and / or the like.

[0173] Another additional step may include hole filling. There is no limitation on the hole filling step and it can be performed in any manner not inconsistent with the objectives described herein. For example, in some embodiments, the holes can be partially or completely coated, treated or filled with hole filling compositions, materials, polymers, gel polymers, layers or depositions (such as PVD). Preferably, the hole filling composition covers 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more of the surface area of ​​the hole. The hole filling composition may include a polymer and a solvent, or consist of or consist essentially of a polymer and a solvent. The solvent may be any suitable solvent for forming a composition for coating or filling holes, including an organic solvent (e.g., octane), water, or a mixture of an organic solvent and water. The polymer may be any suitable polymer, including an acrylate polymer or a polyolefin (including a low molecular weight polyolefin). The polymer content in the hole filling composition can be between 1 and 30%, between 2 and 25%, between 3 and 20%, between 4 and 15%, between 5 and 10%, etc., but not limited thereto, as long as the viscosity of the hole filling composition allows the composition to be coated on the hole walls of any porous biaxially stretched precursor film disclosed herein. The hole filling increases one or both of the machine direction (MD) and transverse direction (TD) stretching.

[0174] Complex, vehicle or equipment

[0175] A composite, comprising a battery separator as described above and one or more electrodes, such as an anode, a cathode, or an anode and a cathode, is configured to be in direct contact therewith. There is no limitation on the type of electrode. For example, the electrode can be those suitable for use in a lithium ion secondary battery.

[0176] Suitable anodes may have an energy capacity greater than or equal to 372 mAh / g, preferably ≥ 700 mAh / g, and most preferably ≥ 1000 mAH / g. The anode is composed of lithium metal foil or lithium alloy foil (e.g., lithium aluminum alloy), or a mixture of lithium metal and / or lithium alloy and materials such as carbon (e.g., coke, graphite), nickel, copper. The anode is not made of only lithium-containing intercalation compounds or lithium-containing insertion compounds.

[0177] Suitable cathodes may be any cathode that is compatible with the anode and may include an intercalation compound, an insertion compound, or an electrochemically active polymer. Suitable intercalation materials include, for example, MoS2, FeS2, MnO2, TiS2, NbSe3, LiCoO2, LiNiO2, LiMn2O4, V6O 13 , V2O5 and CuCl2. Suitable polymers include, for example, polyacetylene, polypyrrole, polyaniline and polythiophene.

[0178] Any of the above separators described herein may be incorporated into any vehicle (eg, an electric car) or device (eg, a cell phone or laptop computer) that is powered in whole or in part by a battery.

[0179] Various embodiments of the present invention have been described to achieve various purposes of the present invention. It should be appreciated that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adjustments will be apparent to those skilled in the art without departing from the spirit and scope of the present invention. Example

[0180] Preparation of Examples

[0181] Products of the invention (multilayer) were prepared and compared to comparative products (trilayer). The multilayer product was formed by the process described herein, comprising the steps of coextruding three separate films comprising three coextruded layers and laminating the three films together. The trilayer product was formed by forming three separate extruded monolayer films and laminating the monolayers together.

[0182] The composition of the micron layer of the prepared product of the present invention is as follows:

[0183] Example 1 (EX 1) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0184] Example 2 (EX 2) - (PP1 / PP2 / PP1) (PE1 / PE2 / PE3) (PP1 / PP2 / PP1) - PP1 is homopolymer PP. PP2 is homopolymer polypropylene with a higher MFR than PP1. PE1 is a high density polyethylene with a melt index between 0.25-0.5 g / 10 min at 2.16 kg and 190°C. PE2 is an ultra high density polyethylene. PE3 is a blend of 95% high density polyethylene and 5% mLLDPE, the high density polyethylene having a melt index between 0.25-0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955-0.966 g / cm 3 between.

[0185] Example 3 (EX 3) - (PP / PP / PP) (PE1 / PE2 / PE1) (PP / PP / PP) - PP layer is made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. PE1 is made of high-density polyethylene, and its melt index is between 0.25-0.5g / 10min at 2.16kg and 190℃. PE2 is made of ultra-high molecular weight polyethylene.

[0186] Example 4 (EX 4) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0187] Example 5 (EX 5) - PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0188] Example 6 (EX 6) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - PP is made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. PE is made of high-density polyethylene, and its melt index is between 0.25-0.5g / 10min at 2.16kg and 190℃.

[0189] Example 7 - (EX 7) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3, MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0190] Example 8 (EX 8) - (PP1 / PP2 / PP1) (PE1 / PE2 / PE1) (PP1 / PP2 / PP1) - PP1 is homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. PP2 is made of homopolymer PP, with MFR of 0.25 and density of 0.9. PE1 is high-density polyethylene, with a melt index between 0.25-0.5g / 10min at 2.16kg and 190°C. PE2 is ultra-high molecular weight polyethylene.

[0191] Example 9 (EX 9) - (PP1 / PP2 / PP1) (PE / PE / PE) (PP1 / PP2 / PP1) - PP1 is made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. PP2 is a blend of 95% homopolymer PP and 5% propylene-ethylene copolymer, the density of homopolymer PP = 0.90g / cm 3 , MFR is in the range of 0.5MFR-2MFR. PE is a blend of 92% high-density polyethylene and 8% olefin block copolymer, and the melt index of the high-density polyethylene is between 0.25-0.5g / 10min at 2.16kg and 190°C.

[0192] Example 10 (EX 10) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0193] Main references Figures 38 to 50 And further multi-layer embodiments, here are further Examples 11 to 38:

[0194] Example 11 - Each PP and PE layer of the three-layer structure itself consists of multiple layers, preferably coextruded and then laminated (PP / PP / PP)(PE / PE / PE)(PP / PP / PP) - all PP layers are made of homopolymer PP, density = 0.90 g / cm 2 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% HDPE and 5% mLLDPE, the melt index of HDPE is between 0.25-0.5g / 10min at 2.16kg and 190°C, and the density ranges from 0.955-0.966g / cm 3 between.

[0195] Example 12 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is a blend or block copolymer that is the same as or different from PP1 and PP2.

[0196] Example 13 - (PP1 / PP1) or (PP2 / PP2) or (PP1 / PP2) - PP1 is a polypropylene blend, PP2 is a PP block copolymer.

[0197] Example 14 - (PP1 / PP1 / PP1) or (PP2 / PP2 / PP2) - PP1 is a polypropylene blend, PP2 is a PP block copolymer.

[0198] Example 15 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0199] Example 16 - (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0200] Example 17 - (PP1 / PP2 / PP3) / (PP3 / PP2 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0201] Example 18 - (PP1 / PP2) / (PP3 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0202] Example 19 - (PP1 / PP2 / PP3 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0203] Example 20 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 includes an adhesion promoter.

[0204] Example 21 - (PO3 / PP2 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PO3 is a polyolefin blend (eg, PP+PE).

[0205] Example 22 - (PP1 / PP2 / PP3) - PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or blocking additives such as silicones. PP2 is homopolymer PP, which is the same or different from the homopolymer PP used in PP1, and includes copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface coefficient of friction (COF) are the same or different from the additives used in PP1.

[0206] Example 23 - (PP3 / PP2 / PP1) - PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or blocking additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP being the same or different from the homopolymer PP used in PP1 and PP3, the copolymer PP being any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP being the same or different from the homopolymer PP in PP1 and PP2, the additives to modify the surface coefficient of friction (COF) being the same or different from the additives used in PP1.

[0207] Example 4 - (PP3 / PP2 / PP1) or (PP1 / PP2 / PP3) - PP1 is homopolymer PP + additives to modify the coefficient of friction (COF) as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + copolymer PP, homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer.

[0208] The composition of the layers of the comparative product may be as follows:

[0209] Comparison - Typical single-layer PP (such as Celgard2500)

[0210] Comparison - Typical three-layer laminate (PP / PE / PP)

[0211] Comparison - Typical single layer PP or typical three layer (PP / PE / PP) typical ceramic coated version

[0212] Example 25: A coextruded PP precursor having the following structure is proposed:

[0213] Homopolymer PP + additives to change surface COF

[0214] Homopolymer PP + Copolymer PP

[0215] Homopolymer PP + additives to change surface COF

[0216] Additives used for surface modification may include any slip or anti-block additives such as silicones. The copolymer may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer or elastomer.

[0217] The coextruded PP precursor can be extruded at any value between 0.9-1.5 blow-up ratio (BUR) to control porosity. The coextruded PP precursor is then sequentially stretched in MD and TD or biaxially stretched simultaneously. The biaxially stretched film can be further calendered to control porosity.

[0218] Example 26: For battery separator or textile applications, the second proposed structure can be as follows:

[0219]

[0220] This structure can be designed for highly curved surface layers and used as a waterproof layer in high-speed water tests.

[0221] The types of copolymers that may be incorporated into the structure include, but are not limited to, propylene-ethylene or ethylene-propylene random copolymers, block copolymers, or elastomers.

[0222] By extruding PP in the form of coextrusion, the surface properties of the PP layer can be changed, and at the same time, a copolymer resin with a lower melting point can be added to the middle layer to reduce the shutdown temperature. Different copolymer resins can also be added anywhere in the structure to control the porosity of the TD stretched film.

[0223] By incorporating BUR in the precursor film, the porosity required for different applications can be further controlled.

[0224] Example 27 - PP1 / PP2 / PP3) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0225] Example 28 - (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 are the same or different PP block copolymers.

[0226] Example 9 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0227] Example 30 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0228] Example 31 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP3 / PP2 / PP1) PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0229] Example 32 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or different PP block copolymer.

[0230] Example 33 - (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) - PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and the copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface coefficient of friction are the same or different from the additives used in PP1.

[0231] Example 34 - (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) - PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP being the same or different from the homopolymer PP used in PP1 and PP3, the copolymer PP being any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP being the same or different from the homopolymer PP in PP1 and PP2, the additives to modify the coefficient of surface friction being the same or different from the additives used in PP1.

[0232] Example 35 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and the copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface coefficient of friction are the same or different from the additives used in PP1.

[0233] Example 36 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface friction coefficient are the same or different from the additives used in PP1.

[0234] Example 37 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP3 / PP2 / PP1) PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and the copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface friction coefficient are the same or different from the additives used in PP1.

[0235] Example 38 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) PP1 is homopolymer PP + additives to modify the coefficient of friction as described herein, which may include any slip or adhesion additives such as silicones. PP2 is homopolymer PP + copolymer PP, the homopolymer PP is the same or different from the homopolymer PP used in PP1 and PP3, and the copolymer PP can be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer. PP3 is homopolymer PP + additives, the homopolymer PP is the same or different from the homopolymer PP in PP1 and PP2, and the additives to modify the surface coefficient of friction are the same or different from the additives used in PP1.

[0236] The composition of the layers of a specific comparative product was prepared as follows:

[0237] Comparative Example 1 (COM EX 1) - (PP) (PE) (PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% high-density polyethylene and 5% mLLDPE, the melt index of high-density polyethylene is 0.25-0.5g / 10min at 2.16kg and 190℃, and the density ranges from 0.955-0.966g / cm 3 between.

[0238] Comparative Example 2 (COM EX 2) - (PP) (PE) (PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% high-density polyethylene and 5% mLLDPE, the melt index of high-density polyethylene is 0.25-0.5g / 10min at 2.16kg and 190℃, and the density ranges from 0.955-0.966g / cm 3between.

[0239] Comparative Example 3 (COM EX 3) - (PP) (PE) (PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% high-density polyethylene and 5% mLLDPE, the melt index of high-density polyethylene is 0.25-0.5g / 10min at 2.16kg and 190℃, and the density ranges from 0.955-0.966g / cm 3 between.

[0240] Comparative Example 4 (COM E X4) - (PP) (PE) (PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% high-density polyethylene and 5% mLLDPE, the melt index of high-density polyethylene is 0.25-0.5g / 10min at 2.16kg and 190℃, and the density ranges from 0.955-0.966g / cm 3 between.

[0241] Comparative Example 5 (COM E X5) - (PP) (PE) (PP) - All PP layers are made of homopolymer PP, density = 0.90 g / cm 3 , MFR is in the range of 0.5MFR-2MFR. All PE layers are made of a blend of 95% high-density polyethylene and 5% mLLDPE, the melt index of high-density polyethylene is 0.25-0.5g / 10min at 2.16kg and 190℃, and the density ranges from 0.955-0.966g / cm 3 between.

[0242] Characterization of Examples - Properties Related to Separator and Battery Performance

[0243] Thickness(μm)

[0244] Thickness was measured in microns μm using an Emveco Microgage 210-A micron thickness tester and test procedure ASTM D374. The thickness of Examples 1-6 and Comparative Examples 1-4 was measured and listed in the tables of Figures 22 and 23. Comparative Examples having thicknesses corresponding to the Examples were prepared so that the separators could be meaningfully compared.

[0245] Basis weight (mg / cm 2 )

[0246] The basis weights of Examples 1-6 and Comparative Examples 1-4 were measured and are listed in the table of FIG. 22 .

[0247] JIS Gurley value (s / 100cc)

[0248] The Gurley value is defined herein as the Japanese Industrial Standard (JIS Gurley value) and is measured using an OHKEN permeability tester. The JIS Gurley value is defined as the time in seconds required for 100 cc of air to pass through a one square inch film under a constant pressure of 4.9 inches of water. The JIS Gurley values ​​of Examples 1-6 and Comparative Examples 1-4 were measured and listed in the table of FIG. 22 .

[0249] MD shrinkage at 105℃ / lhr%

[0250] Shrinkage is measured by placing the test sample between two sheets of paper, which are then clamped together to hold the sample between the papers before being hung in an oven. For the "105°C for 1 hour" test, the sample is placed in an oven at 105°C for 1 hour. After the specified heating time in the oven, each sample is removed and taped to a flat opposing surface with double-sided tape to flatten the sample and smooth the sample for accurate length and width measurements. Shrinkage is measured in the machine direction (MD) and transverse direction (TD) and expressed as MD Shrinkage % and TD Shrinkage %.

[0251] The MD shrinkage of Examples 1-6 and Comparative Examples 1-4 was measured and listed in the table of FIG. 22 .

[0252] MD tensile strength (kgf / cm 2 )

[0253] The tensile strength in the machine direction (MD) was measured using an Instron Model 4201 according to the ASTM-882 protocol. The MD tensile strength of Examples 1-6 and Comparative Examples 1-4 was measured and is listed in the table of FIG.

[0254] MD elongation (%)

[0255] MD Stretch at Break % is the percent elongation of the test sample in the machine direction measured at the maximum tensile strength required for the sample to break. The MD Stretch for Examples 1-6 and Comparative Examples 1-4 was measured and is listed in the table of FIG. 22 .

[0256] TD tensile strength (kgf / cm 2 )

[0257] Transverse direction (TD) tensile strength was measured using an Instron Model 4201 according to the ASTM-882 procedure. The TD tensile strength of Examples 1-6 and Comparative Examples 1-4 was measured and is listed in the table of FIG.

[0258] TD stretching rate (%)

[0259] TD Break % is the percent elongation of the test sample in the transverse direction measured at the maximum tensile strength required for the sample to break. The TD stretch of Examples 1-6 and Comparative Examples 1-4 was measured and listed in the table of FIG. 22 .

[0260] Puncture strength (gf)

[0261] Puncture strength was measured based on ASTM D3763. The measurement was made across the width of the microporous membrane and the puncture strength was defined as the force required to puncture the test sample. The puncture strengths of Examples 1-6 and Comparative Examples 1-4 were measured and listed in the table of FIG. 22 .

[0262] One idea is to use UHMW polymers to improve puncture strength. However, using these polymers with molecular weights greater than 1 million can lead to processing difficulties, especially when the process is such as By utilizing these techniques, the need to use polymers with molecular weights greater than 1M, which can be very difficult to process, especially in dry process membranes, can be reduced.

[0263] DB average(V)

[0264] Voltage is applied to the separator film until dielectric breakdown of the sample is observed. A strong separator shows a high DB. Any non-uniformity in the separator film results in a lower DB value. When used in a battery, a battery separator with a higher average DB, especially a higher minimum DB value, will make the battery safer. The average DB of Examples 1-6 and Comparative Examples 1-4 was measured and listed in the table of Figure 22.

[0265] DB minimum (V)

[0266] Voltage is applied to the separator film until dielectric breakdown of the sample is observed. A strong separator shows a high DB. Any non-uniformity in the separator film results in a lower DB value. When used in a battery, a battery separator with a higher average DB, especially a higher minimum DB value, will make the battery safer. The minimum DB of Examples 1-6 and Comparative Examples 1-4 was measured and listed in the table of Figure 22.

[0267] DB consistency

[0268] The DB values ​​of Examples 1, 4 and 5 were compared with Comparative Examples 1, 2 and 4. The results are shown in Fig.18 Calculate the deviation and list it.

[0269] Mixed penetration average (N)

[0270] Mixed penetration is the force required for the separator to produce a short circuit when the separator is placed between the cathode and anode materials. This test is used to indicate the tendency of the separator to allow short circuits during battery assembly. The details of this method are described in US 2010 / 209758, which is incorporated herein in its entirety. The mixed penetration values ​​for Examples 1-6 and Comparative Examples 1-4 were calculated and listed in the table of Figure 22.

[0271] Nail penetration test

[0272] Examples 1-9 and Comparative Examples 1-5 were tested, and Examples 1 and 6 passed the nail penetration test. None of the comparative examples passed the nail penetration test. The nail penetration test at a speed of 1 cm / second and a speed of 10 cm / second is described in U.S. Patent No. 9,065,152, which is incorporated herein by reference in its entirety.

[0273] Shutdown temperature(℃)

[0274] The resistance reading is 100W×cm 2 The onset shutdown temperature in ° C. was recorded at the same time. The shutdown temperatures of Examples 1-6 and Comparative Examples 1-4 were measured and listed in the table of FIG. 22 .

[0275] Closing speed (ohm-cm 2 )

[0276] The example film was sandwiched between two nickel plates and wetted with PC solvent. The wet separator stack was then subjected to a temperature ramp of 60°C / min. During the test, the resistance between the two nickel plates was monitored with a multimeter. For this test, shutdown was defined as a change in resistance from 100 W x cm 2 Increased by two orders of magnitude to 10,000 W×cm 2 , and normalized by the time required for the resistance to rise. The results of the turn-off speed are expressed in W×cm 2 The closing speeds of Examples 1 to 6 and Comparative Examples 1 to 4 were measured and listed in the table of FIG. 22 .

[0277] ER(ohm-cm 2 )

[0278] The ER method uses an electrolyte solution consisting of a solvent mixture of DI water and 2-propanol. The resistance is evaluated by adding 4 circular separator disks (38mm diameter) in succession between two metal electrodes. The resistance value of the separator is measured in ohms using an LCR meter, which is then multiplied by the area of ​​the electrode to obtain ohm-cm2. The resistivity of the electrolyte is measured using a YSI meter.

[0279] The calculation is as follows:

[0280] 1) Average barrier resistance of continuous barrier layer (Ω) = R 层4 Ω-R层3 Ω+R 层3 Ω-R 层2 Ω / 2

[0281] 2) Electrical impedance, Ω-cm 2 = Average resistance of continuous separator layer, Ω*area of ​​nickel-plated electrode, cm 2

[0282] The QC-ER of Examples 1-6 and Comparative Examples 1-4 were measured and listed in Fig.23 in the table.

[0283] McMillan Number

[0284] The McMillan number is calculated using the electrical impedance (ER) measurement results. The calculation is as follows: McMillan number = (resistance (Ω-cm 2 ) / separator thickness (cm)) / electrolyte resistivity (ohm-cm).

[0285] The McMillan numbers of Examples 1-6 and Comparative Examples 1-4 were measured and listed in Fig.23 in the table.

[0286] Cycle life

[0287] All cycles were completed in constant current (CC) mode. The cathode used was 523NMC. The anode used was high-quality graphite. The electrolyte used was 1M LiPF6 salt in a solvent with a volume ratio of EC:EMC of 3:7. The voltage window was 3.0-4.3V. Cycles 1-5 had a charge rate and discharge rate of C / 10. Cycles 6-10 had a charge rate and discharge rate of C / 5. Cycles 11-15 had a charge rate of C / 5 and a discharge rate of C / 2. Cycles 16-20 had a charge rate of C / 5 and a discharge rate of 1C (charge and discharge rate capacity; 1C is the rate of full charge or discharge in 60 minutes). Cycles 21-25 had a charge rate of C / 5 and a discharge rate of 5C. Cycles 26-30 had a charge rate of C / 5 and a discharge rate of 10C. Cycles 31-35 had a charge rate and discharge rate of C / 10.

[0288] The cycle life of Example 1 and Comparative Example 1 were compared. This was done in a 523NCM vs graphite system with a cutoff of 4.3V at a rate of C / 3. The data shown represent the average of 5 cells per sample (or 10 cells total). The results are shown in Fig.19 Without wishing to be bound by any particular theory, it is believed that the improvement in electrolyte absorption may be due to increased interfaces (e.g., complexity of the lamination interface and pore structure). This test showed a repeatable improvement in the cycle life of the multi-layer product compared to the conventional three-layer.

[0289] Compression elasticity

[0290] The compressive elastic modulus was evaluated using a TMA Q400 and a hemispherical probe. A 5 mm x 5 mm sample was compressed at a constant rate to 1 N (568 N / cm 2 ), and then the pressure was released back to 0 N at a constant rate at ambient temperature. The percentage of dimensional change during compression and recovery was estimated based on the initial thickness of the sample. The compression elasticity of Example 1 and Comparative Example 1 was tested and the results are listed in Figure 5 and Table 1 below.

[0291] Table 1

[0292] sample COMEX1 EX1 Thickness(μm) 12 12 Mix-P(N) 588 653 Compression recovery (%) 3.81 4.47 Maximum compression (%) 13.82 15.20 Final compression (%) 10.01 10.73

[0293] The micro-layer construction provides greater compression recovery than comparable wet process membranes. In certain applications, less crushing and / or better compression recovery may be desired.

[0294] Needle Removal

[0295] Needle removal data in the attachment is collected using a needle removal winder. The machine is equipped with a 45 mm slot roll and the separator roll is screwed into an open needle shaft (4 mm diameter) on the machine. The separator is wound onto the shaft and the needle is pulled apart. The maximum removal force is recorded and measured in Newtons. For each test sample, the outer diameter is held constant and the tension and length of the wound film are varied based on the thickness of the film. It is best to compare films of equal or substantially equal thickness.

[0296] Characterization of Examples - Structural Performance

[0297] AQ porosity (%)

[0298] The porosity of the microporous film samples was measured using ASTM method D-2873 and is defined as the percentage of voids in the microporous film measured in both the machine direction (MD) and the transverse direction (TD). The AQ porosity of Examples 1-6 and Comparative Examples 1-4 was calculated and listed in the table of Figure 22. Some additional porosity data for Example 1 was measured and listed in Table 2 below:

[0299] Table 2

[0300]

[0301] Aquapore porosity (%)

[0302] The Aquapore (AQ) porosity of Examples 1-6 and Comparative Examples 1-4 was measured and listed in Fig.23 in the table.

[0303] AQ PP pore size (μm)

[0304] Pore ​​size in μm was measured using Aquapore available from Porous Materials, Inc (PMI). The AQPP pore sizes for Examples 1-6 and Comparative Examples 1-4 were calculated and are listed in the table of FIG22. Additional data for Examples 1, 9, and 10 were determined and are listed in Table 2.

[0305] AQPE pore size (μm)

[0306] The pore size in μm was measured using Aquapore available from Porous Materials, Inc (PMI). The AQPE pore sizes for Examples 1-6 and Comparative Examples 1-4 were measured and are listed in the table of FIG. 22. Additional data for Examples 1, 9 and 10 were measured and are listed in Table 2.

[0307] AQ surface area (m 2 / g)

[0308] Aquapore is a water pressure measurement technique and is applicable only to testing base membranes. In this measurement, a large area of ​​the membrane is immersed in water and pressurized to 3,000 psi. The results of the Aquapore test are the total porosity of the membrane (expressed in %), the pore size of the PP and / or PE (expressed in μm), and the surface area inside and outside the pores (expressed in mm 2 The AQ surface areas of Examples 1-6 and Comparative Examples 1-4 were measured and are listed in the table of Figure 22. Additional data for Examples 1, 9 and 10 were measured and are listed in Table 2.

[0309] Pore ​​size distribution

[0310] The pore size distribution of Examples 6 and 11 and Comparative Example 4 was measured by mercury intrusion porosimetry. The results are shown in Fig.33 Compared with the embodiments of the present invention, the pore size in Comparative Example 4 is larger and has a narrower distribution.

[0311] The calculated curvature

[0312] The curvature is calculated by the following formula (1):

[0313] N m =T 2 / P (1)

[0314] Among them, N mis the McMillan number, T is the tortuosity, and P is the porosity. Without wishing to be bound by any particular theory, it is believed that battery separators with higher tortuosity will be safer. The reason for this is believed to be that the growth of dendrites between the electrodes will be more difficult because the growing dendrites will have to follow a more tortuous path from the anode to the cathode. The calculated tortuosity for Examples 1-6 and Comparative Examples 1-4 is listed in Fig.23 in the table.

[0315] SEM images

[0316] 1. Conditions

[0317] Procedure for cross-sectional observation by scanning electron microscopy (SEM).

[0318] a.) Cut the sample into suitable size (a few square millimeters).

[0319] b.) Ion milling was performed to produce a flat cross section (MD-ND plane).

[0320] Ion milling machine: E-3500 (Hitachi High-Technologies Corporation)

[0321] Ion source: Ar +

[0322] Accelerating voltage: 3.5 kV

[0323] Discharge voltage: 2.0kV

[0324] Level control: 5 (set value)

[0325] Processing time: 4h

[0326] Temperature: 20-25℃

[0327] c.) Mount the sample on a short post using double-sided carbon conductive tape and carbon paste

[0328] d.) Osmium plasma coating was performed to make the sample conductive.

[0329] 2. SEM observation conditions

[0330] a.) Instrument: S-4800 (Hitachi High-Technologies Corporation)

[0331] Accelerating voltage: 1kV

[0332] Working distance: about 5mm

[0333] SEM images of Examples 1, 2, 4 and 6 and Comparative Examples 1, 4 and 5 were taken. Some of these images show Figure 24-30It is noted that there are clear structural differences between the multi-layer product in the example and the three-layer product in the comparative example. For example, the PP layer of the three-layer product contains more columnar or vertically continuous amorphous regions, while the amorphous regions of the multi-layer PP region (with three PP layers in the example) are mainly non-continuous and non-columnar. Figure 28-30 The side-by-side comparison in shows these differences between multi-layer and three-layer products.

[0334] Machine Learning Testing

[0335] Detailed procedures

[0336] 1: Extract image features to obtain vectors for machine learning

[0337] Use OpenCV python module cv2 to read images

[0338] Get 50 local images of 240x160 pixels^2 at uniform random positions throughout the PP or PE region and normalize the images using cv2.normalize with alpha=0, beta=255, norm_type=cv2.NORM_MINMAX.

[0339] For each local image, use the SIFT feature detector cv2.xfeatures2d.SIFT_create with default settings to get features with angle and size

[0340] · Convert each angle of the obtained feature to a'=90-|mod180-90|

[0341] For i from 1 to 9, count the number of conversion angles a' in the range [10*(i-1), 10*i], which is called bin count.

[0342] Concatenate the 9 bin counts, average the feature size (scalar), and use the feature number (scalar) as its feature vector x k (11 dimensions)(kth image)

[0343] The median of the 11 features in the 50 local images is taken as the feature vector x of the input image.

[0344] Books about the OpenCV python module cv2 include Python Machine Learning by Sebastian Raschka (ISBN 1783555130) and OpenCV with Python Blueprints by Michael Beyeler (1785282697). Both books are incorporated herein by reference in their entirety. For more information about OpenCV, see https: / / en.wikipedia.org / wiki / OpenCV .

[0345] PP layer example:

[0346] ● Obtain the feature vector x from the PP layer using the procedure 1 described above, and normalize each value x in x to x′=(xm) / s using the following mean vector m, where m=[0.121252742025, 0.0932702969461, 0.0637613832138, 0.0471628522627, 0.0410994787666, 0.0455612990903, 0.0663893557564, 0.143913936237, 0.373695714612, 3.4704138 63,569.830508475], and the standard deviation is s = [0.0177890460233, 0.0126226741459, 0.0109280746046, 0.00952236047605, 0.00919810029221, 0.008021674107410.00965575771023, 0.0135729399588, 0.0556357096109, 0.181326979354, 52.6681415756]

[0347] ●Let w be [-2.29884147179, -0.120953660963, 0.609748975014, -0.354807579078, 0.0742943451505, -0.0596756155513, 0.679531409197, 1.18484320645, 0.639551068782, -0.123277373445, 0.495565514875] and calculate the inner product w T x′

[0348] ●If w T x′>-1.27465281948, the image is classified into 9 layers.

[0349] PE layer example:

[0350] ● Obtain the feature vector x from the PE layer using the procedure 1 described above, and normalize each value x in x to x' = (xm) / s using the following mean vector m, where m = [0.0753659021681, 0.0647442404474, 0.052445934828, 0.0441842705626, 0.0424971059836, 0.0495261454071, 0.0745156791392, 0.15315494777, 0.434028151238, 3.51412063 686, 480.02173913], and the standard deviation vector s = [0.0212709138539, 0.0156303526361, 0.0100887199823, 0.00610554172426, 0.00588628646619, 0.00509466227247, 0.00868424601387, 0.0177249443105, 0.0499726205047, 0.217925555283, 60.5317430669]

[0351] Let w be [0.0026717153, -0.2072501509, -0.4883326802, 0.0172248418, -0.5467527574, -0.3892225728, 0.7356477088, 1.1574408691, -1.1992044378, -1.920101147, 0.1068808983, 0.6542173447] and calculate the inner product w T x'

[0352] ●If w T If x'>0.6542173447, the image is classified into 9 layers.

[0353] A machine learning test was performed on Examples 1, 2, 4, 7, 8 and 10 and Comparative Examples 1, 4 and 5 to see whether the comparative examples (three layers) and the examples of the present invention (multi-layers) can be distinguished by this test. The results are shown in Figures 34 to 37 A distinction can be made between comparative examples (three layers) and examples according to the invention (multilayer).

[0354] DSC

[0355] DSC analysis was performed to determine the melting temperature (T m) and the onset of crystallization. A Netzsch DSC 200 F3 apparatus was used with a sealed aluminum sample holder with a porous cover. Nitrogen at 40 ml / min was used as carrier gas to prevent sample oxidation. The mass of the analyzed sample varied from 5 to 6 mg. In order to determine T m The samples were first heat treated to eliminate the thermal history and the onset of crystallization. Next, another heating and cooling cycle starting from 25°C to 300°C was performed at a rate of 10°C / min. Data acquisition and processing were performed using Proteus analysis software. Examples 1, 3, 5 and 6 and Comparative Examples 1, 2, 3 and 4 were evaluated by DSC. The PE layer and the PP layer were evaluated separately. The results are shown in Fig.31 and 32 middle.

[0356] According to at least selected embodiments, the present application, disclosure or invention relates to new or improved membranes, separator membranes, separators, battery separators, secondary lithium battery separators, multilayer membranes, multilayer separator membranes, multilayer separators, multilayer battery separators, multilayer secondary lithium battery separators and / or multilayer battery separators with improved performance, new or improved batteries, capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries and / or secondary lithium ion batteries and / or methods of manufacturing and / or using such membranes, separator membranes, separators, battery separators, secondary lithium battery separators, batteries, capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries and / or secondary lithium ion batteries and / or devices, vehicles or products including them. According to at least specific embodiments, the present disclosure or invention relates to new or improved membrane layers, membranes or separator membranes, battery separators including such membranes and / or related methods. According to at least specific selected embodiments, the present disclosure or invention relates to new or improved porous polymer membranes or separator membranes, battery separators including such membranes and / or related methods. According to at least a particular embodiment, the present disclosure or invention relates to a new or improved microporous polyolefin film or separator film, a microlayer film, a multilayer film including one or more microlayers or nanolayer films, a battery separator including such a film, and / or related methods. According to at least a particular particular embodiment, the present disclosure or invention relates to a new, optimized or improved microporous stretched polymer film or separator film, a microlayer film, a multilayer microporous film or separator film having an outer layer and an inner layer, wherein some layers or sublayers are produced by coextrusion and subsequently laminated together to form a new, optimized or improved film or separator film. In some embodiments, a particular layer, microlayer or nanolayer may comprise a homopolymer, a copolymer, a block copolymer, an elastomer and / or a polymer blend. In a selected embodiment, at least a particular layer, microlayer or nanolayer may comprise a different or different polymer, homopolymer, copolymer, block copolymer, elastomer and / or polymer blend. The present disclosure or invention also relates to new or improved methods of making such films, separator films or separators, and / or methods of using such films, separator films or separators, for example as lithium battery separators. According to at least selected embodiments, the present application or invention is directed to new or improved multilayer and / or micron-layer porous or microporous films, separator films, separators, composites, electrochemical devices and / or batteries and / or methods of making and / or using such films, separators, composites, devices and / or batteries. According to at least particularly selected embodiments, the present application or invention is directed to multilayer new or improved separator films, wherein one or more layers of the multilayer structure are made in a multilayer or micron-layer coextrusion die with multiple extruders. The new or improved film, separator film or separator may preferably exhibit improved shutdown, improved strength, improved dielectric breakdown strength and / or reduced cracking tendency.According to at least selected embodiments, the present application or invention is directed to additives for improving battery performance, improved films containing additives, improved battery separators and / or improved batteries and / or improved or related methods of making and / or using them. According to at least specific embodiments, the present application or invention is directed to films containing additives, separator films and / or battery separators and / or methods of making and / or using such films, separator films and / or battery separators. According to at least a particular embodiment, the present application or invention is directed to incorporating additives into microporous membranes or separator films for secondary lithium batteries (such as secondary lithium ion batteries), improved battery separators and / or related methods. In some embodiments, the membrane may contain additives that improve the chemical properties of the battery (such as a lithium ion battery). In other selected embodiments, the membrane may contain additives that improve needle removal performance, such as siloxane or lithium stearate. In other specific embodiments, the present invention may also relate to methods for making such membranes or separator films and methods for using such membranes or separator films, for example, as battery separators. According to at least selected embodiments, the present application or invention is directed to new or improved porous membranes, separator films, separators, dry process separators, composites, electrochemical devices, batteries and methods of making such membranes, separators, composites, devices and / or batteries. According to at least certain selected embodiments, the present invention is directed to new or improved separator membranes containing additives or elastomers. The improved membranes may preferably exhibit improved shutdown, improved strength, improved dielectric breakdown strength and / or reduced cracking tendency. According to at least certain selected embodiments, the present application or invention is directed to a battery separator having a microporous polymer film or membrane and an optional coating layer on at least one side of the microporous polymer film, wherein at least one of the microporous polymer film and the optional coating layer comprises an additive. The additive may be selected from lubricants, plasticizers, nucleating agents, shrinkage reducing agents, surfactants, SEI improvers, cathode protectants, flame retardant additives, LiPF6 salt stabilizers, overcharge protectors, aluminum corrosion inhibitors, lithium deposition agents or improvers, or solvation enhancers, aluminum corrosion inhibitors, wetting agents, viscosity improvers, friction reducers, COF reducing agents, needle removal reducers, copolymers, block copolymers and / or combinations thereof. In addition, described herein are batteries (including primary or secondary lithium ion batteries) comprising one or more of the described films, membranes, coatings and / or separators. Methods for making films, membranes, coatings and / or battery separators are also described.According to at least a particular embodiment, the present application or invention is directed to an improved or new battery separator having at least one of the following: enhanced puncture strength, reduced needle removal force, improved electrolyte wettability and increased pore size, a microporous polymer film having an optional coating layer on at least one side thereof; a battery separator having at least one of an optional coating and a microporous polymer film, in and / or on which are included additives selected from lubricants, surfactants, nucleating agents, shrinkage reducers and / or plasticizers, the microporous polymer film having additives that are primarily present in at least one surface region of the film, or present throughout the film, in a single surface region of the film, in a first surface region of the film, and in a second surface region of the film opposite to the first surface region; a microporous polymer film surface coated with a coating, the coating may be applied only on one surface of the microporous polymer film, on a first side of the microporous polymer film, while other coatings may be applied on a second side of the microporous polymer film opposite to the first side, and / or combinations thereof. According to at least a possible preferred embodiment, the microporous polymer film or membrane is a microporous polyolefin film, such as a dry-stretched process film, such as a single-layer dry-process film, a two-layer dry-process film, or a multi-layer dry-process film. In addition, according to at least a possible preferred embodiment, one or two or three or four or all five different types of additives can be added to the film, coating or separator, or a single additive can be added as one or two or three or four or all five different types of additives, for example, an additive that is both a lubricant and a surfactant can be added therein or thereon.

[0357] In some embodiments, the microporous multilayer battery separators described herein exhibit improved safety, strength, and durability compared to existing two-layer, three-layer, or multi-layer battery separators. For example, the separators may exhibit increased average dielectric breakdown (DB), increased minimum DB, increased closing speed, and increased bending, all of which indicate safer battery separators. The separators may also exhibit enhanced puncture strength and increased hybrid penetration values, which indicate stronger and more durable batteries.

[0358] These properties of the microporous multilayer battery separators described herein are at least in part the result of the method of making them. In some embodiments, the method includes at least coextruding two or more polymer mixtures to form a first coextruded two-layer, three-layer or multilayer film; coextruding two or more other polymer mixtures to form a second coextruded two-layer, three-layer or multilayer film; and coextruding two or more other polymer mixtures to form a third coextruded two-layer, three-layer or multilayer film. Coextrusion generally involves the use of a coextrusion die having one or more extruders feeding the die (usually one extruder for each layer of the two-layer, three-layer or multilayer film). The polymer mixture used to form each layer of the first, second and third two-layer, three-layer or multilayer film may be the same or different. The mixture may contain only one polymer, or multiple polymers, such as a polymer blend. Moreover, more than three two-layer, three-layer or multilayer films may be formed. After forming the first, second and third two-layer, three-layer or multilayer films, the film is laminated together with two film layers formed on the opposite surface of one of the films to form the microporous battery separator described herein.

[0359] The microporous multilayer battery separators described herein can be used in lithium ion batteries, including secondary lithium batteries, resulting in batteries with improved safety and durability.

[0360] The battery separators herein can be described in several different ways.

[0361] In a first aspect, a battery separator for a lithium battery is described herein. In some embodiments, the battery separator comprises at least one microporous separator membrane or sublayer membrane, which comprises a plurality of porous or microporous polymer microlayers or nanolayers, wherein at least one individual microlayer or nanolayer comprises a different or different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend, comprises a different or different additive, reagent, material and / or filler, or comprises a combination of different or different polymers, molecular weight polymers, homopolymers, copolymers, polymer blends, additives, reagents, materials and / or fillers compared to an adjacent individual microlayer or nanolayer. In some embodiments, the separator membrane or sublayer membrane of a plurality of said polymer microlayers or nanolayers is laminated to each other or to a microporous polymer membrane. In some embodiments, at least one of said separator membrane or sublayer membrane of a polymer microlayer or nanolayer has at least three microlayers or nanolayers. Sometimes, at least one of said separator membrane or sublayer membrane of a polymer microlayer or nanolayer is made of one or more polyolefins. Sometimes, at least one of the separator films or sub-layer films of the polymer micro-layer or nano-layer is composed of a co-extruded dry process polyolefin micro-layer or nano-layer. In some embodiments, at least two of the separator films or sub-layer films of the polymer micro-layer or nano-layer are used. In some embodiments, at least three of the separator films or sub-layer films of the polymer micro-layer or nano-layer are used.

[0362] Described herein are multi-layer microporous films or membranes that can exhibit improved performance, including improved dielectric breakdown and strength, compared to existing single-layer or three-layer microporous membranes of the same thickness. Preferred multi-layer microporous membranes comprise micron layers and one or more laminated barriers. Also disclosed are battery separators or batteries comprising one or more multi-layer microporous films or membranes. Compared to batteries and battery separators using existing single-layer and three-layer microporous membranes, the batteries and battery separators of the present invention are preferably safer and stronger. Additionally, methods for making the multi-layer microporous separators, membranes or films described herein are described herein.

[0363] To achieve the various purposes of the present invention, various embodiments of the present invention have been described. It should be appreciated that these embodiments are merely illustrative of the principles of the present invention. It will be apparent to those skilled in the art that various modifications and adjustments may be made without departing from the spirit and scope of the present invention.

[0364] Without departing from the spirit and essential attributes of the invention, the present invention may be implemented in other forms, and therefore, when indicating the scope of the invention, reference should be made to the appended claims rather than the foregoing description. Components that can be used to implement the disclosed methods and systems are disclosed. These components and other components are disclosed herein, and it should be understood that for all methods and systems, when disclosing combinations, subsets, interactions, groups, etc. of these components, although specific reference to each of their different individual and collective combinations and permutations may not be explicitly disclosed, each is specifically considered and described herein. This applies to all aspects of the present application, including but not limited to the steps in the disclosed methods. Therefore, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed using any specific embodiment or combination of embodiments of the disclosed methods.

[0365] The foregoing written description of the structure and method is given for illustrative purposes only. The embodiments are used to disclose exemplary implementations, including the best mode, and methods that enable those skilled in the art to implement the present invention (including making and using any device or system and performing any combination). These embodiments are not intended to be exhaustive or limit the present invention to the precise steps and / or forms disclosed, and there may be many modifications and changes according to the teachings of the foregoing. The features described herein may be combined in any combination. The steps of the method described herein may be performed in any order that is physically possible. The patentable scope of the present invention is defined by the appended claims and may include other embodiments that occur to those skilled in the art. If these other embodiments have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims, these other embodiments are intended to be within the scope of the claims.

[0366] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein. Various modifications of the compositions and methods other than those shown and described herein are intended to fall within the scope of the appended claims. In addition, although only certain representative compositions and method steps disclosed herein are specifically described, other combinations of compositions and method steps are also intended to fall within the scope of the appended claims, even if not specifically set forth. Thus, combinations of steps, elements, components, or components may be referred to herein, either explicitly or less explicitly, however, other steps, elements, components, or components are also included even if not explicitly stated.

[0367] When used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly indicates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value, and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from a particular value and / or to another particular value. Similarly, when a numerical value is expressed as an approximation by using the antecedent "about", it should be understood that the particular value forms another embodiment. It should be further understood that the endpoints of each range are important relative to the other endpoint and are independent of the other endpoint. "Optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes situations where the event or situation occurs and situations where the event or situation does not occur.

[0368] Throughout the specification and claims of this specification, the word "comprising" and variations of the word, such as "participle form comprising" and "singular form comprising", mean "including but not limited to", and are not intended to exclude, for example, other additives, components, integers or steps. The terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, and they are also disclosed. "Exemplary" or "for example" means "an example" and is not intended to convey the meaning that it is a preferred or ideal embodiment. Similarly, "such as" is not used in a restrictive sense, but is used for illustration or exemplary purposes.

[0369] Unless otherwise noted, all numbers indicating geometric shapes, dimensions, and the like used in the specification and claims are not intended to limit the application of the doctrine of equivalents to the scope of the claims and should at least be understood as being interpreted in light of significant digits and ordinary rounding techniques.

[0370] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs.Publications cited herein and the materials they cite are expressly incorporated herein by reference.

[0371] Furthermore, the invention illustratively disclosed herein suitably may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. A battery separator for a lithium battery, comprising: at least one microporous membrane or sublayer comprising a plurality of porous or microporous polymer micro- or nano-layers, wherein: At least one individual micro-layer or nano-layer comprises a different polymer, molecular weight polymer, homopolymer, copolymer and / or polymer blend than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; The microporous membrane or sub-layer membrane comprises at least 9 layers, forming at least 8 interfaces; the thickness of at least three continuous layers is 0.1 to 2 microns each; At least three consecutive layers are coextruded and then laminated with at least one other layer; The microporous membrane or sublayer membrane has a puncture strength of 290 gf or more; Each of the plurality of porous or microporous polymer micro-layers or nano-layers is made of dry coextruded micro-layers or nano-layers; the minimum dielectric breakdown value of the at least one microporous separator is greater than that of a three-layer microporous film having the same thickness, Gurley value and / or porosity; At least one micron layer or nano layer of the outermost layer comprises lithium stearate, calcium stearate, PE beads and silicone.

2. The battery separator according to claim 1, wherein A plurality of said sub-layer films are laminated to each other or to a microporous polymer film.

3. The battery separator according to claim 1, wherein: At least one sub-layer membrane of the microporous membrane is laminated with another sub-layer membrane of the microporous membrane.

4. The battery separator according to claim 1, wherein At least one of the sub-layer films is made of one or more polyolefins.

5. The battery separator according to claim 1, wherein: It comprises at least two of the microporous membranes.

6. The battery separator according to claim 1, wherein: It contains at least three of the microporous membranes.

7. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein At least one of the microporous separators has a higher average dielectric breakdown value (V) than the average dielectric breakdown value of three microporous films having the same thickness, Gurley value and / or porosity; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone. A lithium battery comprising the battery separator according to claim 1 .

9. A lithium battery comprising the battery separator according to claim 7.

10. A lithium battery comprising the battery separator according to claim 5.

11. A lithium battery comprising the battery separator according to claim 2.

12. A lithium battery comprising the battery separator according to claim 3.

13. A secondary lithium battery comprising the battery separator according to claim 1.

14. A lithium ion battery comprising the battery separator according to claim 1.

15. The battery separator of claim 1, wherein: At least three continuous sub-layer films have an A / B / A structure, A is a polypropylene homopolymer, and B is a polypropylene blend.

16. The battery separator of claim 15, wherein: The thickness of at least three continuous sub-layers of a microporous separator is 0.1-2.0 microns.

17. The battery separator of claim 16, wherein: The thickness of at least three continuous sub-layers of the membranes in two adjacent microporous membranes is 0.1 to 2.0 microns.

18. The battery separator of claim 15, wherein: The multi-layer sub-layer film has a thickness of 1 micron to 30 microns.

19. The battery separator of claim 18, wherein: The multi-layer sub-layer film has a thickness of 1 micron to 20 microns.

20. The battery separator of claim 19, wherein: The multi-layer sub-layer film has a thickness of 1 micron to 15 microns.

21. The battery separator of claim 20, wherein: The multi-layer sub-layer film has a thickness of 1 micron to 10 microns.

22. The battery separator of claim 15, wherein: In one of the sub-layer films, at least three continuous layers are coextruded layers.

23. The battery separator of claim 22, wherein: The coextruded at least three consecutive layers are then laminated with at least one other layer to form a microporous polymer film.

24. The battery separator of claim 23, wherein: At least one other layer is a coextruded layer.

25. The battery separator of claim 15, wherein: At least three consecutive layers comprise a polyolefin or a polyolefin blend.

26. The battery separator of claim 25, wherein: Each of the at least three consecutive layers comprises polyethylene.

27. The battery separator of claim 25, wherein: Each of the at least three consecutive layers comprises polypropylene.

28. The battery separator of claim 15, wherein: The at least one microporous separator or sublayer membrane comprises 12 or more layers.

29. The battery separator of claim 28, wherein: The at least one microporous separator or sublayer membrane comprises 15 or more layers.

30. The battery separator of claim 29, wherein: The at least one microporous separator or sublayer membrane comprises 18 or more layers.

31. The battery separator of claim 30, wherein: The at least one microporous separator or sublayer membrane comprises 21 or more layers.

32. The battery separator of claim 31, wherein: The at least one microporous separator or sublayer membrane comprises 24 or more layers.

33. The battery separator of claim 32, wherein: The at least one microporous separator or sublayer membrane comprises 27 or more layers.

34. The battery separator of claim 33, wherein: The at least one microporous separator or sublayer membrane comprises 30 or more layers.

35. The battery separator of claim 15, wherein: At least one of the microporous membranes or sublayer membranes has a puncture strength of 290 gf or greater.

36. The battery separator of claim 35, wherein: At least one of the microporous separators or sublayer membranes has a puncture strength of 300 gf or greater.

37. The battery separator of claim 36, wherein: At least one of the microporous separators or sublayer membranes has a puncture strength of 310 gf or greater.

38. A battery comprising one or more battery separators as claimed in claim 15.

39. A method for forming a battery separator, the battery separator comprising at least one sub-layer microporous membrane, which comprises a plurality of micro-layers or nano-layers coextruded by a dry process, at least one individual micro-layer or nano-layer comprising a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprising different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers, forming at least 8 interfaces; at least three continuous layers each having a thickness of 0.1 to 2 microns; at least three continuous layers are coextruded and then laminated with at least one other layer; The sublayer film has a puncture strength of at least 290 gf, Compared with the battery separator of the same thickness in the past, the membrane is divided into more layers, but each layer is thinner, the method comprising: coextruding at least three layers by dry process; and laminating at least two or three coextruded layers with at least one other layer to form a multi-layer microporous membrane; The outermost layer comprises at least one micro-layer or nano-layer comprising lithium stearate, calcium stearate, PE beads and silicone.

40. The method of claim 39, wherein: At least four layers are coextruded.

41. The method of claim 40, wherein: At least five layers are coextruded.

42. The method of claim 41, wherein: At least six layers are coextruded.

43. The method of claim 42, wherein: At least seven layers are coextruded.

44. The method of claim 43, wherein: At least eight layers are coextruded.

45. The method of claim 44, wherein: At least nine layers are coextruded.

46. ​​The method of claim 45, wherein: At least ten layers are coextruded.

47. The method of claim 39, wherein: At least one other layer is a coextruded layer.

48. The method of claim 39, wherein: At least one other layer is a single extrusion layer.

49. The method of claim 39, wherein: At least two coextruded layers are laminated to two other layers.

50. The method of claim 49, wherein: One of the two other layers is laminated on a first side of the at least two coextruded layers, and a second of the two other layers is laminated on a side opposite to the first side of the at least two coextruded layers.

51. The method of claim 49, wherein: At least one of the two other layers is a coextruded layer.

52. The method of claim 51, wherein: Both other layers are coextruded layers.

53. The method of claim 50, wherein: At least one of the two other layers is a coextruded layer.

54. The method of claim 53, wherein: Both other layers are coextruded layers.

55. The method of claim 39, wherein: At least two of the coextruded layers and at least one other layer comprise a polyolefin or a polyolefin blend.

56. The method of claim 53, wherein: At least one of the at least two coextruded layers comprises a different polyolefin or polyolefin blend than that comprised by the other layer.

57. The method of claim 54, wherein: At least one of the at least two coextruded layers comprises polypropylene and the other layer comprises polyethylene.

58. The method of claim 57, wherein: At least one of the at least two coextruded layers comprises polyethylene; the other layer comprises polypropylene.

59. The method of claim 49, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

60. The method of claim 50, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

61. The method of claim 51, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

62. The method of claim 52, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

63. The method of claim 53, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

64. The method of claim 54, wherein: The two other layers each comprise polypropylene or each comprise polyethylene.

65. The method of claim 51, wherein: At least one of the two other layers is a coextruded layer coextruded with at least two other layers.

66. The method of claim 65, wherein: At least one of the two other layers is a coextruded layer coextruded with at least three other layers.

67. The method of claim 66, wherein: At least one of the two other layers is a coextruded layer coextruded with at least four other layers.

68. The method of claim 67, wherein: At least one of the two other layers is a coextruded layer coextruded with at least five other layers.

69. The method of claim 68, wherein: At least one of the two other layers is a coextruded layer coextruded with at least six other layers.

70. The method of claim 69, wherein: At least one of the two other layers is a coextruded layer coextruded with at least seven other layers.

71. The method of claim 70, wherein: At least one of the two other layers is a coextruded layer coextruded with at least eight other layers.

72. The method of claim 71, wherein: At least one of the two other layers is a coextruded layer coextruded with at least nine other layers.

73. The method of claim 52, wherein: At least one of the two other layers is a coextruded layer coextruded with at least two other layers.

74. The method of claim 73, wherein: At least one of the two other layers is a coextruded layer coextruded with at least three other layers.

75. The method of claim 74, wherein: At least one of the two other layers is a coextruded layer coextruded with at least four other layers.

76. The method of claim 75, wherein: At least one of the two other layers is a coextruded layer coextruded with at least five other layers.

77. The method of claim 76, wherein: At least one of the two other layers is a coextruded layer coextruded with at least six other layers.

78. The method of claim 77, wherein: At least one of the two other layers is a coextruded layer coextruded with at least seven other layers.

79. The method of claim 78, wherein: At least one of the two other layers is a coextruded layer coextruded with at least eight other layers.

80. The method of claim 79, wherein: At least one of the two other layers is a coextruded layer coextruded with at least nine other layers.

81. The method of claim 53, wherein: At least one of the two other layers is a coextruded layer coextruded with at least two other layers.

82. The method of claim 81, wherein: At least one of the two other layers is a coextruded layer coextruded with at least three other layers.

83. The method of claim 82, wherein: At least one of the two other layers is a coextruded layer coextruded with at least four other layers.

84. The method of claim 83, wherein: At least one of the two other layers is a coextruded layer coextruded with at least five other layers.

85. The method of claim 84, wherein: At least one of the two other layers is a coextruded layer coextruded with at least six other layers.

86. The method of claim 85, wherein: At least one of the two other layers is a coextruded layer coextruded with at least seven other layers.

87. The method of claim 86, wherein: At least one of the two other layers is a coextruded layer coextruded with at least eight other layers.

88. The method of claim 87, wherein: At least one of the two other layers is a coextruded layer coextruded with at least nine other layers.

89. The method of claim 54, wherein: At least one of the two other layers is a coextruded layer coextruded with at least two other layers.

90. The method of claim 89, wherein: At least one of the two other layers is a coextruded layer coextruded with at least three other layers.

91. The method of claim 90, wherein: At least one of the two other layers is a coextruded layer coextruded with at least four other layers.

92. The method of claim 91, wherein: At least one of the two other layers is a coextruded layer coextruded with at least five other layers.

93. The method of claim 92, wherein: At least one of the two other layers is a coextruded layer coextruded with at least six other layers.

94. The method of claim 93, wherein: At least one of the two other layers is a coextruded layer coextruded with at least seven other layers.

95. The method of claim 94, wherein: At least one of the two other layers is a coextruded layer coextruded with at least eight other layers.

96. The method of claim 95, wherein: At least one of the two other layers is a coextruded layer coextruded with at least nine other layers.

97. A battery separator made by the method of claim 39.

98. The battery separator of claim 1, comprising: A first region of two or more layers, wherein When the film is observed in the z-direction by SEM, the first region comprises a discontinuous amorphous region; as well as A second region of at least one layer, wherein the second region comprises two or more layers when observed in the Z direction of the film using a SEM, and the maximum width of the amorphous region is 0.8 micrometers.

99. The battery separator of claim 98, wherein: The maximum width of the amorphous region was 0.7 μm.

100. The battery separator of claim 99, wherein: The maximum width of the amorphous region was 0.6 μm.

101. The battery separator of claim 97, wherein: 50% or more of the amorphous region in the first region is non-continuous.

102. The battery separator of claim 97, wherein: The first region and / or the second region comprises one or more layers comprising a polyolefin; and / or, 60% or more of the amorphous regions in the first region are non-continuous.

103. The battery separator of claim 97, wherein: The first region comprises at least one layer comprising polyethylene and the second region comprises at least one layer comprising polypropylene, and / or 70% or more of the amorphous regions in the first region are non-continuous.

104. The battery separator of claim 97, wherein: At least one of the first region and the second region comprises a coextruded two-layer, three-layer or more-layer film, and / or 80% or more of the amorphous regions in the first region are non-continuous.

105. The battery separator of claim 104, wherein: The first region comprises a coextruded film of two, three or more layers, and / or 90% or more of the amorphous regions in the first region are non-continuous.

106. The battery separator of claim 104, wherein: The first region and the second region comprise a coextruded two-layer film, a three-layer film, or a film having more than three layers.

107. The battery separator of claim 104, wherein: Each of the first region, the second region, and the third region of the microporous multilayer battery separator comprises a coextruded two, three, or more than three layers of film.

108. The battery separator of claim 104, wherein: At least one of the second and third regions of the microporous multilayer battery separator comprises a coextruded two, three, or more than three layers of film.

109. The battery separator of claim 108, wherein The second zone comprises coextruded films of two, three or more layers.

110. The battery separator of claim 108, wherein: The third zone comprises coextrusion of two, three or more layers of film.

111. The battery separator of claim 1, wherein: The at least one microporous separator or sub-layer membrane has a higher average dielectric breakdown value (V) and / or a minimum dielectric breakdown value that is 3 to 20% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

112. The battery separator of claim 1, 7 or 111, wherein: At least one microporous separator or sub-layer membrane has an average dielectric breakdown value (V) that is 1 to 35% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

113. The battery separator of claim 112, wherein: At least one microporous separator or sub-layer membrane has an average dielectric breakdown value (V) that is 5 to 35% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

114. The battery separator of claim 113, wherein: At least one microporous separator or sub-layer membrane has an average dielectric breakdown value (V) that is 10 to 35% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

115. The battery separator of claim 114, wherein: At least one microporous separator or sub-layer membrane has an average dielectric breakdown value (V) that is 15 to 35% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

116. The battery separator of claim 115, wherein: At least one microporous separator or sub-layer membrane has an average dielectric breakdown value (V) that is 20 to 35% higher than a three-layer microporous film having the same thickness, Gurley value and / or porosity.

117. The battery separator of claim 111, wherein At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

118. The battery separator of claim 112, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

119. The battery separator of claim 113, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

120. The battery separator of claim 114, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

121. The battery separator of claim 115, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

122. The battery separator of claim 116, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 5 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

123. The battery separator of claim 111, wherein: At least one of the microporous separators or sub-layers has a minimum dielectric breakdown value that is 10 to 15% higher than a three-layer microporous film having the same thickness, Gurley value, and / or porosity.

124. The battery separator of claim 111 or 117, wherein: There are nine or more layers in at least one microporous separator.

125. The battery separator of claim 111, wherein: There are twelve or more layers in at least one microporous separator.

126. The battery separator of claim 117, wherein: There are twelve or more layers in at least one microporous separator.

127. The battery separator of claim 111, wherein: Fifteen or more layers are present in at least one microporous separator.

128. The battery separator of claim 117, wherein: Fifteen or more layers are present in at least one microporous separator.

129. The battery separator of claim 111, wherein: Eighteen or more layers are present in at least one microporous separator.

130. The battery separator of claim 117, wherein: Eighteen or more layers are present in at least one microporous separator.

131. The battery separator of claim 111, wherein: Twenty or more layers are present in at least one microporous membrane.

132. The battery separator of claim 117, wherein: Twenty or more layers are present in at least one microporous membrane.

133. The battery separator of claim 111, wherein: The at least one microporous separator is present in twenty-four or more layers.

134. The battery separator of claim 117, wherein: The at least one microporous separator is present in twenty-four or more layers.

135. The battery separator of claim 111, wherein: The at least one microporous separator has twenty seven or more layers.

136. The battery separator of claim 117, wherein: The at least one microporous separator has twenty seven or more layers.

137. The battery separator of claim 111, wherein: The at least one microporous separator has thirty or more layers.

138. The battery separator of claim 117, wherein: The at least one microporous separator has thirty or more layers.

139. The battery separator of claim 111, wherein: At least one layer of at least one microporous separator comprises a polyolefin.

140. The battery separator of claim 117, wherein: At least one layer of at least one microporous separator comprises a polyolefin or a polyolefin blend.

141. The battery separator of claim 139, wherein: At least one layer of at least one microporous separator comprises polyethylene or a polyethylene blend.

142. The battery separator of claim 140, wherein: At least one layer of at least one microporous separator comprises polyethylene or a polyethylene blend.

143. The battery separator of claim 139, wherein: At least one layer of at least one microporous separator comprises polypropylene or a polypropylene blend.

144. The battery separator of claim 140, wherein: At least one layer of at least one microporous separator comprises polypropylene or a polypropylene blend.

145. The battery separator of claim 139, wherein: At least one layer of at least one microporous separator comprises polypropylene or a polypropylene blend, and at least one layer comprises polyethylene or a polyethylene blend.

146. The battery separator of claim 111, wherein At least one microporous membrane or sub-membrane comprises: a first region of two or more layers, wherein the first region comprises polypropylene and is a non-continuous amorphous region when viewed in the z-direction of the film using a SEM; and A second region of at least one layer.

147. The battery separator of claim 117, wherein: At least one microporous membrane or sub-membrane comprises: a first region of two or more layers, wherein the first region comprises polypropylene and is a non-continuous amorphous region when viewed in the z-direction of the film using a SEM; and A second region of at least one layer.

148. The battery separator of claim 111, wherein At least one microporous membrane or sub-membrane comprises: a first region of two or more layers, wherein the first region comprises polypropylene and is a non-continuous amorphous region when viewed along the z-direction of the film using a SEM; a second region of at least one layer; and A third region of at least one layer.

149. The battery separator of claim 117, wherein: At least one microporous membrane or sub-membrane comprises: a first region of two or more layers, wherein the first region comprises polypropylene and is a non-continuous amorphous region when viewed in the z-direction of the film with a SEMz; a second region of at least one layer; and A third region of at least one layer.

150. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein At least one microporous membrane or sub-membrane exhibits a peak mercury intrusion value of 5 mL / g or less in log differential mercury intrusion when measured by mercury intrusion porosimetry; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

151. The battery separator of claim 150, wherein The peak mercury pressure value is a logarithmic differential mercury pressure of 4.5 mL / g or less.

152. The battery separator of claim 151, wherein The peak mercury pressure value is a logarithmic differential mercury pressure of 4 mL / g or less.

153. The battery separator of claim 152, wherein The peak mercury pressure value is a logarithmic differential mercury pressure of 3.5 mL / g or less.

154. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein comprising a multi-layer microporous film having a MacMillan number of 5 or more; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

155. The battery separator of claim 154, wherein: The McMillan number is above 5.

5.

156. The battery separator of claim 155, wherein: The McMillan number is 6 or more.

157. The battery separator of claim 156, wherein: The McMillan number is 7 or more.

158. The battery separator of claim 157, wherein: The McMillan number is above 7.

5.

159. The battery separator of claim 158, wherein The McMillan number is 8 or more.

160. The battery separator of claim 159, wherein: The McMillan number is 9 or more.

161. The battery separator of claim 160, wherein: The McMillan number is 10 or more.

162. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein A multi-layer microporous film having more layers than previous battery separators of the same thickness, but each layer is thinner and has a curvature value of 1.6 or higher; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

163. The battery separator of claim 162, wherein: The curvature value is 1.7 or higher.

164. The battery separator of claim 163, wherein: The curvature value is 2.0 or higher.

165. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers each having a thickness of 0.1 to 2 microns; at least three continuous layers are coextruded and then laminated with at least one other layer; The sublayer film has a puncture strength of at least 290 gf, wherein Comprising a multi-layer microporous film having a needle removal force of less than 50 N; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

166. The battery separator of claim 165, wherein The needle removal force is less than 40 N.

167. The battery separator of claim 166, wherein The needle removal force is less than 30 N.

168. The battery separator of claim 167, wherein The needle removal force is less than 20 N.

169. The battery separator of claim 168, wherein The needle removal force is less than 15 N.

170. The battery separator of claim 168, wherein The needle removal force is less than 10 N.

171. A battery separator comprising a dry coextruded multi-layer microporous film comprising: a first region comprising two or more layers; a second region comprising two or more layers on a first side of the first region; and a third region comprising two or more layers on a side opposite to the first side of the first region, in, At least one of the first, second or third regions comprises PE and has a lower crystallinity when measured by DSC than a PE-containing layer of a three-layer microporous film, wherein the three-layer microporous film has the same thickness as the multi-layer microporous film; The battery separator comprises at least one sub-layer microporous membrane, which comprises a plurality of micro-layers or nano-layers co-extruded by a dry process, at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight compared to an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers, forming at least 8 interfaces; the thickness of at least three continuous layers is 0.1 to 2 microns each; at least three continuous layers are co-extruded and then laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, and the outermost layer of the battery separator comprises at least one micro-layer or nano-layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

172. The battery separator of claim 171, wherein: The crystallinity is 1 to 20% lower.

173. The battery separator of claim 171, wherein: The crystallinity is 1 to 17% lower.

174. The battery separator of claim 171, wherein: The crystallinity is 1 to 10% lower.

175. The battery separator of claim 171, wherein: The crystallinity is 1 to 5% lower.

176. A battery separator comprising a multi-layer microporous film, comprising at least one sub-layer microporous membrane, comprising a plurality of dry coextruded micro-layers or nano-layers, at least one individual micro-layer or nano-layer comprising a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprising different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers, forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein, comprising at least two regions or sublayers, each comprising at least two micron layers, and having a mixed permeability (N) value greater than 380 N; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

177. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 400 N.

178. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 450 N.

179. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 500 N.

180. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 550 N.

181. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 600 N.

182. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 650 N.

183. The battery separator of claim 176, wherein: The mixed penetration (N) value is greater than 700 N.

184. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein, Contains a multi-layer microporous film having a resistivity of less than or equal to 2.0; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

185. The battery separator of claim 184, wherein: The resistance is less than or equal to 1.

7.

186. The battery separator of claim 185, wherein: The resistance is less than or equal to 1.

6.

187. The battery separator of claim 186, wherein: The resistance is less than or equal to 1.

5.

188. The battery separator of claim 187, wherein: The resistance is less than or equal to 1.

4.

189. The battery separator of claim 188, wherein The resistance is less than or equal to 1.

3.

190. The battery separator of claim 184, wherein: The resistance is less than or equal to 1.

2.

191. The battery separator of claim 184, wherein: The resistance is less than or equal to 1.

1.

192. The battery separator of claim 184, wherein: The resistance is less than or equal to 1.

0.

193. A battery separator comprising at least one sub-layer microporous membrane comprising a plurality of dry coextruded micro-layers or nano-layers, wherein at least one individual micro-layer or nano-layer comprises a polymer, homopolymer, copolymer and / or polymer blend having a different molecular weight than an adjacent individual micro-layer or nano-layer; and / or comprises different additives, agents and / or fillers; the sub-layer membrane comprises at least 9 layers forming at least 8 interfaces; at least three continuous layers are each 0.1 to 2 microns thick; at least three continuous layers are coextruded and laminated with at least one other layer; the sub-layer membrane has a puncture strength of at least 290 gf, wherein, A microporous multilayer film comprising dry coextrusion followed by lamination, having a lower dielectric breakdown standard deviation value than a three-layer microporous film having the same thickness, Gurley value and / or porosity as the multilayer microporous film; The outermost layer thereof comprises at least one micron layer or nano layer, and comprises lithium stearate, calcium stearate, PE beads and silicone.

194. The battery separator of claim 193, wherein: The standard deviation values ​​were 10 to 60% lower.

195. The battery separator of claim 193, wherein: The standard deviation values ​​were 10 to 40% lower.

196. The battery separator of claim 193, wherein: The standard deviation values ​​were 10 to 20% lower.

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