Microporous membranes, films, and related methods

Abstract

There is a need for new and improved multilayer microporous membranes, base films, or battery separators that have various improvements over conventional membranes, base films, or battery separators.SOLUTION: Described herein are multilayer microporous films or membranes that may exhibit improved properties, including improved dielectric breakdown and strength, as compared to prior single-layer or three-layer microporous membranes of the same thickness. Preferred multilayer microporous membranes comprise microlayers and one or more laminated interfaces or barriers. Also disclosed are battery separators or batteries comprising one or more of the multi-layer microporous films or membranes.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] 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 having improved properties, 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 making 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 same, and / or methods of testing, quantifying, characterizing and / or analyzing such membranes, separator membranes, separators, battery separators, and the like. According to at least certain 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 certain 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 certain embodiments, the present disclosure or invention relates to new or improved microporous polyolefin membranes or separator membranes, microlayer membranes, multilayer membranes including one or more microlayer or nanolayer membranes, battery separators including such membranes, and / or related methods. According to at least certain specific embodiments, the present disclosure or invention relates to novel, optimized or improved microporous stretched polymeric membranes or separator membranes having one or more novel or improved outer and / or inner layers, microlayer membranes, multilayer microporous membranes or separator membranes having outer and inner layers, some of which layers or sublayers are produced by coextrusion and then laminated together to form the novel, optimized or improved membrane or separator membrane.In some embodiments, certain layers, microlayers, or nanolayers may comprise homopolymers, copolymers, block copolymers, elastomers, and / or polymer blends. In selected embodiments, at least certain layers, microlayers, or nanolayers may comprise different or distinct polymers, homopolymers, copolymers, block copolymers, elastomers, and / or polymer blends. The present disclosure or invention also relates to new or improved methods of making such membranes, separator membranes, or separators and / or methods of using such membranes, separator membranes, 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 microlayer porous or microporous membranes, separator membranes, separators, composites, electrochemical devices, and / or batteries, and / or methods of making and / or using such membranes, separators, composites, devices, and / or batteries. According to at least certain selected embodiments, the present application or invention is directed to new or improved separator membranes that are multilayered, where one or more layers of the multilayer structure are produced in a multilayer or microlayer coextrusion die by multiple extruders. The new or improved membranes, separators, or separators may preferably demonstrate new or improved structures, performance, or applications, such as improved shutdown, improved strength, improved dielectric breakdown strength, improved elongation, improved puncture strength, improved high-speed puncture strength, lower Gurley, reduced crystallization, and / or reduced tear tendency, and combinations thereof. [Background technology]

[0002] Known methods for making microporous bi- or tri-layer membranes, for example for use as battery separator membranes, include laminating or adhering two or more monolayer precursors together or coextruding more than one layer of the membrane simultaneously using a coextrusion die. Such methods are described, for example, in U.S. Pat. Nos. 5,629,599; 5,729,503; 5,729,503; and 5,729,503.

[0003] The above methods may not fully optimize the balance of strength and / or performance characteristics for use in certain primary and / or secondary battery applications, such as lithium-ion rechargeable batteries. This is especially true as battery separator requirements become more stringent as consumers desire thinner and stronger battery separators. For example, microporous tri-layer membranes formed by co-extrusion of three layers may have reduced strength. Separators formed by laminating single layers may also ultimately be unable to meet the ever-increasing demand. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 5,952,120 [Patent Document 2] US Patent Application Publication No. 2014 / 0079980 [Patent Document 3] U.S. Patent No. 5,223,032 [Patent Document 4] U.S. Patent No. 5,240,655 [Patent Document 5] US Patent Application Publication No. 2005 / 031943 Summary of the Invention [Problem to be solved by the invention]

[0005] There is a need for new and improved multi-layer microporous membranes, base films, or battery separators that offer various improvements over conventional membranes, base films, or battery separators. [Means for solving the problem]

[0006] According to at least selected embodiments, the present application, disclosure or invention may address the above-mentioned needs, challenges or problems and / or may 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, 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 making 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 same, and / or methods of testing, quantifying, characterizing and / or analyzing such membranes, separator membranes, separators, battery separators, and the like having improved properties. According to at least certain embodiments, the present disclosure or invention relates to new or improved membrane layers, membranes or separator films, battery separators including such membranes, and / or related methods. According to at least certain selected embodiments, the present disclosure or invention relates to new or improved porous polymer membranes or separator films, battery separators including such membranes, and / or related methods. According to at least certain embodiments, the present disclosure or invention relates to new or improved microporous polyolefin membranes or separator membranes, microlayer membranes, multilayer membranes including one or more microlayers or nanolayers, battery separators including such membranes, and / or related methods. According to at least certain embodiments, the present disclosure or invention relates to new, optimized, or improved microporous expanded polyolefin membranes having one or more new or improved outer and / or inner layers. The present disclosure relates to polymer or separator membranes, microlayer membranes, multilayer microporous membranes or separator membranes having outer and inner layers, some of which are produced by coextrusion and then laminated together to form new, optimized, or improved membranes or separator membranes. In some embodiments, certain layers, microlayers, or nanolayers may comprise homopolymers, copolymers, random copolymers, PP and / or PE copolymers, block copolymers, elastomers, and / or polymer blends. In select embodiments, at least certain layers, microlayers, or nanolayers may comprise different or distinct polymers, homopolymers, copolymers, block copolymers, elastomers, and / or polymer blends. The present disclosure or invention also relates to new or improved methods of making such membranes, separator membranes, or separators and / or methods of using such membranes, separator membranes, 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 microlayer porous or microporous membranes, separator membranes, separators, composites, electrochemical devices, and / or batteries, and / or methods of making and / or using such membranes, separators, composites, devices, and / or batteries. According to at least certain selected embodiments, the present application or invention is directed to new or improved separator membranes that are multilayered, where one or more layers of the multilayer structure are produced in a multilayer or microlayer coextrusion die by multiple extruders. The new or improved membranes, separator membranes, or separators may preferably demonstrate new or improved structures, performance, and applications, such as improved shutdown, improved strength, improved dielectric breakdown strength, improved elongation, improved puncture strength, improved high-speed puncture strength, lower Gurley, reduced crystallization, and / or reduced tear tendency, and combinations thereof.

[0007] The microporous multi-layer battery separators described herein, in some embodiments, exhibit improved safety, strength, and durability compared to prior bi-layer, tri-layer, or multi-layer battery separators.

[0008] These properties of the microporous multilayer battery separators described herein are at least partially a result of the method by which they are made. In some embodiments, this method includes at least coextruding two or more polymer mixtures to form a first coextruded bi-, tri-, or multilayer film, coextruding two or more other polymer mixtures to form a second coextruded bi-, tri-, or multilayer film, and coextruding two or more additional polymer mixtures to form a third coextruded bi-, tri-, or multilayer film. Coextrusion typically involves using a coextrusion die with one or more extruders (typically one extruder per layer of the bi-, tri-, or multilayer film) feeding the die. The polymer mixtures used to form each layer of the first, second, and third bi-, tri-, or multilayer films can be the same or different. The mixtures can include only one polymer or more than one polymer, e.g., polymer blends. Also, more than three bi-, tri-, or multilayer films can be formed. After the first, second, and third bilayer, trilayer, or multilayer films are formed, the films are laminated together with two of the films formed on opposing surfaces of one of the films to form the optionally preferred microporous battery separator described herein.

[0009] The microporous multilayer battery separators described herein can be used in lithium ion batteries, including secondary lithium batteries, to result in batteries with improved safety and durability. The battery separators herein may be described in several different ways.

[0010] In one embodiment, a multilayer microporous membrane or film has: (a) at least one additive in at least one layer of the multilayer microporous membrane or film; (b) has or exhibits increased or improved elasticity at 150°C or greater compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin configuration as the multilayer microporous membrane or film; (c) has or exhibits increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin configuration as the multilayer microporous membrane or film; (d) has or exhibits increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin configuration as the multilayer microporous membrane or film. (e) having or exhibiting reduced high temperature shrinkage at 150°C compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film; (f) having or exhibiting reduced high temperature shrinkage at 120°C compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film; (g) having at least one layer comprising a polymer blend; (h) having a nonwoven or woven fabric attached to one or both sides of the multilayer microporous membrane or film; (i) and combinations thereof.

[0011] In some embodiments, the microporous membrane or film has at least one additive in at least one layer thereof. In some embodiments, at least one additive is present in one or both outermost layers of the multilayer microporous membrane or film. Sometimes, at least one additive is present in one of the outermost layers of the multilayer microporous membrane or film. Sometimes, an additive is present in both outermost layers of the multilayer microporous membrane or film. Sometimes, an additive is present in at least one inner layer of the multilayer microporous membrane or film. Sometimes, an additive is present in at least one of the two outer layers and at least one inner layer of the multilayer microporous film or membrane. In some preferred embodiments, each layer of the multilayer microporous membrane or film has a different composition from each adjacent layer. In some embodiments, the multilayer microporous membrane may be coated on one or both sides.

[0012] The additive may include a polymer additive. For example, the additive may include a functional polymer, such as a maleic anhydride-modified polymer. Examples of maleic anhydride-modified polymers include maleic anhydride-modified homopolymer polypropylene, copolymer polypropylene, high-density polypropylene, or low-density polypropylene. Other examples of maleic anhydride-modified polymers include maleic anhydride-modified homopolymer polyethylene, copolymer polyethylene, high-density polyethylene, or low-density polyethylene. In other embodiments, the additive may include an ionomer. For example, this may include a Li-, Na-, or Zn-based ionomer. In other embodiments, the additive may include cellulose nanoparticles. Sometimes, the additive may include inorganic particles having a narrow particle size distribution. For example, the inorganic particles may be selected from at least one of SiO2 particles, TiO2 particles, or a mixture thereof. In other embodiments, the additive may include a lubricant.

[0013] The lubricants or lubricating oils described herein are not particularly limited. As understood by those skilled in the art, lubricants are compounds that act to reduce friction between a variety of different surfaces, including the following: polymer:polymer; polymer:metal; polymer; organic materials; and polymer:inorganic materials. Specific examples of the lubricants or lubricating oils described herein are compounds containing siloxy functional groups, including siloxanes and polysiloxanes, and fatty acid salts, including metal stearates.

[0014] Compounds containing two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more siloxy groups may be used as lubricants as described herein. Siloxanes, as understood by those skilled in the art, are a class of molecules having a backbone of alternating silicon (Si) and oxygen (O) atoms, each of which may have an attached hydrogen (H) or saturated or unsaturated organic group, such as —CH3 or —CH5. Polysiloxanes are polymerized siloxanes, typically having higher molecular weights. In some preferred embodiments described herein, the polysiloxanes may be high molecular weight, or even more preferably, in some cases, ultra-high molecular weight polysiloxanes. In some embodiments, high and ultra-high molecular weight polysiloxanes may have a weight average molecular weight ranging from 500,000 to 1,000,000.

[0015] The fatty acid salts described herein are also not particularly limited and may be any fatty acid salt that functions as a lubricant (preferably without damaging battery function). The fatty acid of the fatty acid salt may be a fatty acid having 12 to 22 carbon atoms. For example, the metal fatty acid may be selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, behenic acid, erucic acid, and arachidic acid. The metal is not particularly limited, but in preferred embodiments, it is an alkali or alkaline earth metal, such as Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, and Ra. In some preferred embodiments, the metal is Li, Be, Na, Mg, K, or Ca.

[0016] In some preferred embodiments, the fatty acid salt is lithium stearate, sodium stearate, lithium oleate, sodium oleate, sodium palmitate, lithium palmitate, potassium stearate, or potassium oleate.

[0017] In some preferred embodiments described herein, lubricating oils incorporating the fatty acid salts described herein have melting points of 200°C (or 200 degrees Celsius) or higher, 210°C or higher, 220°C or higher, 230°C or higher, or 240°C or higher. Fatty acid salts, such as lithium stearate (melting point of 220°C) or sodium stearate (melting point of 245-255°C), have such melting points. Fatty acid salts, such as calcium stearate (melting point of 155°C), do not. The inventors of this application have found that calcium stearate may be less ideal from a processing standpoint than other fatty acid metal salts, such as metal stearates, which have higher melting points, especially at high loading levels. In particular, they have found that calcium stearate cannot be added in amounts greater than 800 ppm without experiencing what is known as the "dusting effect," in which wax separates and becomes ubiquitous during the hot extrusion process. Without wishing to be bound by any particular theory, the use of fatty acid metal salts with melting points above the hot extrusion temperature is believed to solve this "dusting" problem. Fatty acid salts with melting points higher than calcium stearate, particularly those with melting points above 200°C, can be incorporated in amounts of 1% or greater than 1,000 ppm without "dusting." Amounts of 1% or greater have been found to be important for achieving desired properties, such as improved wetting and improved pin removal. Amounts of 1,000 to 10,000 ppm, 1,000 to 8,000 ppm, 1,000 to 9,000 ppm, 1,000 to 7,000 ppm, 1,000 to 6,000 ppm, 1,000 to 5,000 ppm, 1,000 to 4,000 ppm, 1,000 to 3,000 ppm, or 1,000 to 2,000 ppm are particularly preferred for this purpose in some embodiments.

[0018] In some other preferred embodiments, the fatty acid salts described herein may be water-soluble. Water-soluble, as used herein, refers to the ability of lubricating oils, e.g., fatty acid salts, to react with steroids. The metal fatty acid has a solubility in water equal to or greater than that of lithium stearate, that is, the metal fatty acid has the same solubility in water as lithium stearate or is more soluble in water than lithium stearate.

[0019] The lubricant may be amphiphilic. The lubricant may also be a fatty acid salt, such as a fatty acid salt selected from lithium stearate and sodium stearate. In some embodiments, the lubricant is a compound containing one or more siloxy functional groups, including siloxanes and polysiloxanes. In some embodiments, the lubricant may be an ultra-high molecular weight polysiloxane. In some embodiments, the additive may include at least one of a nucleating agent, a cavitation promoter, a fluoropolymer (e.g., PVDF), a crosslinking agent, an x-ray detectable material (e.g., barium sulfate), a lithium halide (e.g., lithium iodide), a polymer processing agent, a high temperature melt index (HTMI) polymer (e.g., PMP, PMMA, PET, PVDF, aramid, syndiotactic polystyrene, and combinations thereof), an electrolyte additive (e.g., an SEI improver, a cathode protectant, a flame retardant additive, a LiPF salt stabilizer, an overcharge protectant, an aluminum corrosion inhibitor, a lithium precipitation agent or improver, or at least one selected from the group consisting of a solvation promoter, an aluminum corrosion inhibitor, a wetting agent, and a thickener), and combinations thereof.

[0020] In some embodiments, the multilayer membrane or film has or exhibits increased or improved elasticity compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multilayer microporous membrane or film. In some embodiments, the tangent(delta) (or tangent delta) of the membrane or film is greater than -0.6 at 150°C as measured by dynamic mechanical analysis. In some embodiments, the tangent(delta) of the membrane or film is between -1.0 and -0.6 at temperatures between 175°C and 200°C as measured by dynamic mechanical analysis. In some embodiments, the tangent(delta) is between -0.9 and -0.6 at temperatures between 175°C and 200°C. In some embodiments, the tangent(delta) is between -0.8 and -0.6 at temperatures between 175°C and 200°C. In some embodiments, the tangent(delta) is between -0.7 and -0.6 at temperatures between 175°C and 200°C. In some embodiments, the tangent(delta) of the membrane or film, as measured by dynamic mechanical analysis, is greater than -1.2 at temperatures of 200°C or greater. In some embodiments, the tangent(delta) is greater than -1.0 at temperatures of 200°C or greater. In some embodiments, the tangent(delta) is greater than -0.8 at temperatures of 200°C or greater.

[0021] In another embodiment, the microporous membrane or film has or exhibits increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multi-layer microporous membrane or film. In some embodiments, the % Recovery is greater than 9%, greater than 9.5%, greater than 10.0%, greater than 10.1%, greater than 10.2%, greater than 10.3%, greater than 10.4%, or greater than 10.5% as measured by the Compression Recovery Method.

[0022] In another embodiment, the microporous membrane or film has or exhibits an increased or improved elongation at break (TD) compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multi-layer microporous membrane or film. In some embodiments, the elongation at break (TD) is greater than 30% higher, greater than 35% higher, greater than 40% higher, greater than 41% higher, greater than 42% higher, greater than 43% higher, greater than 44% higher, greater than 45% higher, greater than 46% higher, greater than 47% higher, greater than 48% higher, greater than 49% higher, greater than 50% higher, greater than 51% higher, greater than 52% higher, greater than 53% higher, greater than 54% higher, greater than 55% higher, greater than 56% higher, greater than 57% higher, greater than 58% higher, greater than 59% higher, greater than 60% higher, greater than 61% higher, greater than 62% higher, greater than 63% higher, greater than 64% higher, greater than 65% higher, greater than 66% higher, greater than 67% higher, greater than 68% higher, greater than 69% higher, greater than 70% higher, greater than 71% higher, greater than 72% higher, greater than 73% higher, greater than 74% higher, greater than 75% higher, greater than 76% higher, greater than 77% higher, greater than 78% higher, greater than 79% higher, greater than 80% higher, greater than 81% higher, greater than 82% higher, greater than 83% higher, greater than 84% higher, greater than 85% higher, greater than 86% higher, greater than 87% higher, greater than 88% higher, greater than 89% higher, greater than 90% higher, greater than 91 High or more than 45% high.

[0023] In another embodiment, the microporous membrane or film has a high temperature shrinkage at 120°C that is 30-75% lower, 35-70% lower, 35-65% lower, or 40-60% lower than a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multilayer microporous membrane or film.

[0024] In another embodiment, at least one layer of the microporous membrane or film comprises a polymer blend. The at least one layer may be an outer layer in some embodiments, or may be an inner layer in some embodiments. In some embodiments, at least one outer layer and at least one inner layer may comprise a polymer blend. The blend may be, in some embodiments, at least two different polyolefins, at least two different polyethylenes, or at least two different polypropylenes. In some embodiments, the blend may be at least one polyethylene and at least one polypropylene. In some embodiments, the polymer blend may comprise a polyolefin and a non-polyolefin.

[0025] In another embodiment, the microporous membrane or film may have a nonwoven or woven fabric attached to one or both sides of the membrane or film.

[0026] In some embodiments, the total thickness of the membrane or film is less than 30 microns, less than 25 microns, less than 20 microns, less than 15 microns, or less than 10 microns. In some embodiments, the microporous membrane or film may comprise at least three layers, all of which are microlayers (1-10 microns thick), all of which are nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers; at least four layers, all of which are microlayers (1-10 microns thick), all of which are nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers; at least five layers, all of which are microlayers (1-10 microns thick), all of which are nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers; or at least six layers, all of which are microlayers (1-10 microns thick), all of which are nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers.

[0027] In another aspect, a multilayer microporous film is disclosed, the multilayer microporous film comprising two or more layers and polyethylene in one or more of the layers, wherein when the region is tested by the machine learning test described herein, the following is satisfied: W T x ' ≧-2.0 or W T x ' ≧-1.0.

[0028] In some embodiments, the following is met: W T x ' ≧0.0 or W T x ' ≧2.0.

[0029] In another aspect, a multilayer microporous film is disclosed, the multilayer microporous film comprising a region comprising two or more layers and polypropylene in one or more of the layers, wherein the region, when tested by the machine learning test described herein, satisfies the following: W T x ' ≧-1.5 or WT x ' ≧-1.0.

[0030] In some embodiments, the following is met: W T x ' ≧0.5 or W T x ' ≧1.5.

[0031] In another aspect, a multilayer microporous film is disclosed, comprising: (1) two outermost sub-membranes comprising three or more nanolayers (less than 1 micron thick) or microlayers (between 1 and 10 microns thick); and (2) at least one inner sub-membrane comprising three or more nanolayers (less than 1 micron thick) or microlayers (between 1 and 10 microns thick) comprising, consisting of, or consisting essentially of polypropylene. In some embodiments, in at least one or both of the outermost sub-membranes, the outermost microlayer or nanolayer comprises, consists of, or consists essentially of polyethylene. In some embodiments, in at least one or both of the outermost sub-membranes, the innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend. In some embodiments, in at least one outermost sub-membrane, the outermost microlayer or nanolayer comprises, consists of, or consists essentially of polyethylene, and the innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend. In some embodiments, in both outermost sub-membranes, the outermost microlayer or nanolayer comprises, consists of, or consists essentially of polyethylene, and the innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend. In some embodiments, at least one inner sub-membrane is in direct contact with at least one of the outermost sub-membranes, e.g., one of the outermost sub-membranes has its innermost microlayer or nanolayer comprise, consist of, or consist essentially of a polyethylene blend. In some embodiments, the film or membrane includes another inner sub-membrane comprising at least three nanolayers or microlayers, and at least one of the outermost microlayers or nanolayers of the other inner sub-membrane comprises, consists of, or consists essentially of a polyethylene blend. In some embodiments, the nanolayer or microlayer of the outermost sub-membrane is thinner than the nanolayer or microlayer of the innermost sub-membrane. In some embodiments, they are 2 to 5 times thinner, 3 to 5 times thinner, or 4 to 5 times thinner.In some embodiments, the film or membrane comprises 10-35% or 15-25% polyethylene, based on the total weight of the membrane or film. One embodiment described in the preceding paragraph is shown in Figure 64.

[0032] In another aspect, a multilayer microporous membrane or film is disclosed, comprising: (1) two outermost sub-membranes comprising at least three nanolayers (less than 1 micron thick) or microlayers (1-10 microns thick) (or two outermost nanolayers or microlayers and at least one inner nanolayer or microlayer), wherein the two outermost nanolayers or microlayers of the outermost sub-membranes are thinner than at least one inner nanolayer or microlayer of the outermost sub-membranes; and (2) at least one inner sub-membrane comprising at least three nanolayers or microlayers (or two outermost nanolayers or microlayers and at least one inner nanolayer or microlayer), wherein the two outermost nanolayers or microlayers of at least one inner sub-membrane are thinner than at least one inner nanolayer or microlayer of the at least one inner sub-membrane. In some embodiments, the two outermost nano- or micro-layers of the outermost sub-membrane are 10-95%, 50-90%, 60-90%, 70-90%, or 80-90% thinner than at least one inner nano- or micro-layer of the outermost sub-membrane. In some embodiments, the two outermost nano- or micro-layers of at least one inner sub-membrane are 10-95%, 50-90%, 60-90%, 70-90%, or 80-90% thinner than at least one inner nano- or micro-layer of at least one inner sub-membrane. In some embodiments, the outermost nano- or micro-layer of the outermost sub-membrane comprises, consists of, or consists essentially of polyethylene. In some embodiments, the outermost nano- or micro-layer of at least one inner sub-membrane comprises, consists of, or consists essentially of polyethylene. In some embodiments, the inner nano- or micro-layer of at least one outermost sub-membrane comprises, consists of, or consists essentially of polypropylene. consisting essentially of. In some embodiments, the polypropylene is a high molecular weight polypropylene. In some embodiments, the multilayer microporous membranes or films described herein comprise 10-35 wt% polyethylene, based on the total weight of the membrane or film. In some embodiments, the outer sub-membranes and at least one inner sub-membrane are each separately formed by coextrusion. After separately forming the sub-membranes by coextrusion, each of the sub-membranes can be laminated to at least one other sub-membrane to form the multilayer microporous membrane or film. One embodiment described in the preceding paragraph is shown in Figure 54.

[0033] In another embodiment, a multilayer microporous film is disclosed, comprising: (1) two outermost sub-membranes comprising two outermost nano- or micro-layers (less than 1 micron thick) and at least one inner nano- or micro-layer, wherein the outermost nano- or micro-layers of the two outermost sub-membranes comprise, consist of, or consist essentially of polyethylene, and at least one inner nano- or micro-layer of the two outermost sub-membranes comprises, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene; and (2) at least one inner sub-membrane comprising two outermost nano- or micro-layers and at least one inner nano- or micro-layer, wherein the two outermost nano- or micro-layers of at least one inner sub-membrane comprise, consist of, or consist essentially of polyethylene, and at least one inner nano- or micro-layer of at least one inner sub-membrane comprises, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene. In some embodiments, the outermost sub-membrane of at least one inner sub-membrane comprises two or more, three or more, four or more, or five or more nano- or micro-layers. In some embodiments, all of the inner nano- or micro-layers comprise, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene. In some embodiments, the multilayer microporous film or layer comprises 10-35 wt. % or 15-25 wt. % polyethylene, based on the total weight of the membrane or film. In some embodiments, the sub-membranes are formed by coextrusion, and in some embodiments, after formation of the sub-membranes by coextrusion, each sub-membrane is laminated to at least one other sub-membrane to form the microporous membrane or film. One embodiment described in the preceding paragraph is shown in Figure 55.

[0034] In another aspect, a multilayer microporous membrane or film includes: (1) two outermost sub-membranes comprising two or more nanolayers (less than 1 micron thick) or microlayers (1-10 microns thick), wherein the outermost nanolayer or microlayer of the outermost sub-membrane, which is also the outermost nanolayer or microlayer of the multilayer microporous membrane or film, comprises a polysiloxane; and (2) at least one inner sub-membrane comprising two or more nanolayers or microlayers. In some embodiments, the amount of polysiloxane or siloxane is 1-10 wt % or 1-3 wt %, based on the total weight of the nanolayer or microlayer of the outermost sub-membrane in which the polysiloxane or siloxane is present. In some embodiments, there are two inner sub-membranes, and the inner and outermost sub-membranes each have three or more microlayers or nanolayers. These are embodiments of 12 or more microlayers or nanolayers. In some embodiments with 12 or more microlayers or nanolayers, the outermost nanolayers or microlayers of each inner sub-membrane may be in contact with one another and comprise, consist of, or consist essentially of the same resin. In some embodiments, they have the same composition. In some embodiments with 12 or more microlayers or nanolayers, the outermost nanolayers or microlayers of each inner sub-membrane are in contact with the outermost nanolayers or microlayers of the outermost sub-membrane and each inner sub-membrane comprises, consists of, or consists essentially of the same resin as the outermost nanolayers or microlayers of the outermost sub-membrane with which it is in contact. In some embodiments, they have the same composition. In some embodiments, there is one inner sub-membrane, and the inner sub-membrane and the outermost sub-membrane each have six or more microlayers or nanolayers. These are embodiments with 18 or more microlayers or nanolayers. In some embodiments with 18 or more microlayers or nanolayers, both outermost microlayers or nanolayers of the outermost sub-membrane comprise a siloxane or polysiloxane or siloxane. In some embodiments with 18 or more microlayers or nanolayers, the siloxane or polysiloxane is present in an amount of 1 to 10 wt % or 1 to 3 wt %, based on the total weight of the microlayers or nanolayers in which the siloxane or polysiloxane is contained. In some embodiments with 18 or more microlayers or nanolayers, the outermost microlayer or nanolayer of the outermost sub-membrane also comprises polypropylene in addition to the siloxane or polysiloxane. In some embodiments with 18 or more microlayers or nanolayers, the outermost microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of polypropylene. In some 18 or more microlayer or nanolayer embodiments, the inner microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of at least one of polypropylene, polypropylene blend, polyethylene, or polyethylene blend. In some 18 or more microlayer or nanolayer embodiments, the inner microlayer or nanolayer of the inner sub-membrane comprises, in that order, a PP microlayer or nanolayer, a PE blend microlayer or nanolayer, a PE blend microlayer or nanolayer, and a PP microlayer or nanolayer. In some 18 or more microlayer or nanolayer embodiments, the inner microlayer or nanolayer of the outermost sub-membrane comprises, consists of, or consists essentially of at least one of polypropylene, polypropylene blend, polyethylene, or polyethylene blend. In some 18 or more microlayer or nanolayer embodiments, the inner microlayer or nanolayer of the outermost sub-membrane comprises, in that order, a PP microlayer or nanolayer, a PE blend microlayer or nanolayer, a PE blend microlayer or nanolayer, and a PP microlayer or nanolayer.In some embodiments, there are three or more inner sub-membranes, and each of the inner and outermost sub-membranes has three or more microlayers or nanolayers. These are 15 or more microlayer or nanolayer embodiments. In some embodiments, the inner and outermost sub-membranes have only three microlayers or nanolayers. These are 15 microlayer or nanolayer embodiments. In these 15 microlayer or nanolayer embodiments, each inner sub-membrane may comprise, consist of, or consist essentially of polyethylene. In some embodiments, each of the microlayers or nanolayers of two inner sub-membranes consists of, or consists essentially of, polyethylene. In some 15 microlayer or nanolayer embodiments, each of the nanolayers or microlayers of one of the inner sub-membranes comprises, consists of, or consists essentially of polypropylene. In some 15 microlayer or nanolayer embodiments, one inner sub-membrane having a nanolayer or microlayer comprising, consisting of, or consisting essentially of polypropylene comprises, in that order, a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend, a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend, and a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend. In some 15 microlayer or nanolayer embodiments, two inner sub-membranes having nanolayers or microlayers comprising, consisting of, or consisting essentially of polyethylene and one inner sub-membrane having a nanolayer or microlayer comprising, consisting of, or consisting essentially of polypropylene are arranged in the following order: sub-membrane having nanolayers or microlayers comprising, consisting of, or consisting essentially of polyethylene; sub-membrane having nanolayers or microlayers comprising, consisting of, or consisting essentially of polypropylene; sub-membrane having nanolayers or microlayers comprising, consisting of, or consisting essentially of polyethylene.In some embodiments of 15 or more microlayers or nanolayers, the nanolayers or microlayers of the outermost sub-membrane may each individually be made of polypropylene only, a blend of polypropylene and another resin, or polypropylene and polypropylene. In some embodiments of 15 or more microlayers or nanolayers, the outermost sub-membrane comprises, consists of, or consists essentially of a blend of polypropylene and polysiloxane, a nanolayer or microlayer of polypropylene, and a nanolayer or microlayer of a blend of polypropylene and another resin, in that order. In some embodiments, the polysiloxane or siloxane-containing membrane or film comprises 10-30 wt % or 15-25 wt % polyethylene, based on the total weight of the membrane or film.

[0035] In some embodiments, the polysiloxane or siloxane-containing membranes or films described herein have microlayers or nanolayers that all have the same thickness or that have different thicknesses. In some embodiments, the polysiloxane or siloxane-containing membranes or films described herein are made by forming each sub-membrane using coextrusion. In some embodiments, each coextruded sub-membrane is then laminated to at least one other coextruded sub-membrane to form the membrane or film. One embodiment described in the preceding paragraph is shown in Figures 56-59.

[0036] In another aspect, a multilayer microporous membrane or film comprises: (1) two outermost sub-membranes comprising six or more nanolayers (having a thickness of less than 1 micron) or microlayers (having a thickness between 1 and 10 microns); and (2) at least one inner sub-membrane comprising six or more nanolayers or microlayers. In some embodiments, there is one inner sub-membrane, and the inner sub-membrane and the two outermost sub-membranes each comprise six microlayers or nanolayers. This is an 18-layer embodiment. In some 18-layer embodiments, the outermost microlayer or nanolayer of the outermost sub-membrane comprises, consists of, or consists essentially of polypropylene. In some 18-layer embodiments, the outermost microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of a blend of polypropylene and another resin. In some 18-layer embodiments, the two microlayers or nanolayers intermediate the two outermost sub-membranes and the inner sub-membrane comprise, consist of, or consist essentially of polyethylene. In some embodiments, the two middle microlayers or nanolayers of the two outermost sub-membranes are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the two outermost sub-membranes there is one microlayer or nanolayer comprising, consisting of, or consisting essentially of a blend comprising polypropylene and another resin. In some 18-layer embodiments, the two middle microlayers or nanolayers of the inner sub-membrane are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the inner sub-membrane there is one nanolayer or microlayer comprising, consisting of, or consisting essentially of polypropylene. In some embodiments, this is, for example, a polypropylene blend with polypropylene and a propylene-ethylene elastomer. In some embodiments, all of the microlayers or nanolayers have the same thickness, and in some embodiments, they do not. In some embodiments, the above-described multilayer membranes or films are formed by coextrusion of each of the sub-membranes, and in some embodiments, by laminating each sub-membrane to at least one other sub-membrane.In some embodiments, the multi-layer microporous membrane comprises 10-35 wt. % polyethylene, preferably 15-25 wt. % polyethylene, based on the total weight of the membrane or film. One embodiment described in the preceding paragraphs is shown in Figure 60.

[0037] In another aspect, a battery separator comprises, consists of, or consists essentially of any multilayer microporous membrane described herein. In some embodiments, the membrane or film is coated on one or two sides. In some embodiments, the coating comprises inorganic or organic particles and polymeric bilayers. The ceramic coating comprises, consists of, or consists essentially of metal.

[0038] In another aspect, a battery including the battery separator described herein is described.

[0039] In another aspect, a vehicle or device is described that includes a battery described herein.

[0040] In yet another embodiment, a woven fabric comprising, consisting of, or consisting essentially of at least one multilayer microporous membrane or film described herein.

[0041] In yet another aspect, described are textiles comprising, consisting of, or consisting essentially of at least one multi-layer microporous membrane or film described herein and a nonwoven or woven fabric. In some embodiments, the nonwoven or woven fabric is attached to the multi-layer microporous membrane or film.

[0042] In another aspect, a method for forming a multilayer microporous membrane or film is described herein. The method includes at least the steps of coextruding at least two layers and laminating the at least two coextruded layers to one other layer, or in some embodiments, 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 one of the at least two other layers, is a coextruded layer. In some embodiments, at least one of the other layers is a monoextruded layer. In embodiments in which at least two coextruded layers are laminated to two other layers, sometimes one of the two other layers is laminated to a first side of the at least two coextruded layers, and a second of the two other layers is laminated to a side of the at least two coextruded layers opposite the first side. At least one of the two other layers can be a coextruded layer. In some embodiments, both of the two other layers are coextruded layers. In some embodiments, at least one of the at least two coextruded layers and the other layer comprise a polyolefin or a polyolefin blend. For example, they may comprise polyethylene or a polyethylene blend or polypropylene or a polypropylene blend. In some embodiments, at least one of the at least two coextruded layers comprises polyethylene, and at least one or both of the other layers comprise polypropylene or a polyethylene blend. In some embodiments, at least one of the at least two coextruded layers comprises polyethylene, and at least one or both of the other layers comprise polypropylene or a polypropylene blend. In some embodiments, each of the two other layers comprises polyethylene or a polyethylene blend. In some embodiments, each of the two other layers comprises polypropylene or a polypropylene blend.In some embodiments, one or both of the two other layers is a coextruded layer, 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 the layer is coextruded with 9 other layers, the total number of coextruded layers is 10.

[0043] In another aspect, a method for producing a multi-layer microporous membrane comprising at least one additive in at least one layer is disclosed. In some embodiments, the method comprises co-extruding the additive-containing polymer mixture with at least one other polymer mixture to form a co-extruded precursor film. In other embodiments, the method comprises co-extruding the additive-containing polymer mixture with at least one other polymer mixture to form a co-extruded precursor film. and another step of laminating the mono-extruded precursor film to at least one other film. The lamination may include the application of at least one of heat, pressure, or a combination thereof. The method of forming a co-extruded precursor film may include the additional step of laminating the co-extruded precursor film to at least one other film.

[0044] In another aspect, described herein are multilayer microporous membranes that exhibit an increased puncture average (g) when tested at a high puncture rate greater than 25 mm / min compared to the puncture average (g) at 25 mm / min. In some embodiments, the high puncture rate can be 100 mm / min. The puncture average (g) at 100 mm / min can be 20 g higher, 30 g higher, 40 g higher, or 50 g higher than the puncture average (g) measured at 25 mm / min. In some embodiments, the multilayer membranes described herein have an average puncture of greater than 250 g at 25 mm / min, greater than 275 g at 25 mm / min, greater than 300 g at 25 mm / min, greater than 325 g at 25 mm / min, or greater than 350 g at 25 mm / min. In some embodiments, the thickness of the multilayer microporous membrane can be 14 to 30 microns.

[0045] In another aspect, a multilayer microporous membrane formed by a collapsed-cell method is disclosed. The microporous membrane formed by the collapsed-cell method has a thickness of less than 14 microns and a puncture strength of greater than 200 g. In some embodiments, the thickness is 6-12 microns, and sometimes the thickness is about 10 microns. In some embodiments, the puncture strength is 210 g or greater, 220 g or greater, 230 g or greater, or 240 g or greater.

[0046] Microporous membranes formed by the collapsed bubble method can have structures formed by collapsing bubbles, including coextruded PP / PP / PE, PP / PE / PE, PP / PP, PE / PE, PE / PP, PE / PP / PP, or PP / PE / PP / PE. The microporous membranes can include discernible interfaces formed when the bubbles collapse when cross-sectional SEM images are taken.

[0047] In some embodiments, the microporous membrane has a low Gurley, for example, less than 250, less than 225, less than 200, less than 190, less than 180, or less than 175 (s / 100cc).

[0048] In some embodiments, the microporous membrane comprises polyethylene having a melt flow rate of 0.1 to 10 g / min. The microporous membrane may have at least one layer comprising polyethylene having a thickness of at least 1.75 microns. In some embodiments, the layer comprising polyethylene has a thickness of at least 2 microns. In some embodiments, the layer comprising polyethylene has a thickness of less than 1.75 microns.

[0049] In some embodiments, the membrane comprises polypropylene having a melt flow rate of 0.01 to 10 g / 10 min, 0.1 to 5 g / 10 min, or 0.01 to 2.5 g / 10 min, as measured by ASTM D1238-13 and / or ISO 1133-1:2011. [Brief explanation of the drawings]

[0050] [Figure 1] FIG. 1 is a partial cross-sectional scanning electron micrograph (SEM) at 2,500x magnification of an exemplary laminated three-layer or triplex three-layer microporous membrane of the present invention, 3layer / 3layer / 3layer (having nine coextruded microlayers per layer of each three-layer and three microlayers per each PP or PE sublayer of each three-layer layer) (at least the outer PP layer of each layer is microporous). [Figure 2] Figure 2 is a partial cross-sectional scanning electron micrograph (SEM) at 15,000x magnification of a portion of the polypropylene surface sublayer (three microlayers of PP) of the surface three-layer component or sub-membrane of the composite laminate membrane of Figure 1 (the PP sublayer is magnified and is actually three coextruded PP microlayers whose interfaces are difficult to discern). [Figure 3] Figure 3 is a partial cross-sectional scanning electron micrograph (SEM) at 15,000x magnification of the polyethylene sublayer (three microlayers of PE) of one of the three layers of nine microlayers of the three-layer membrane of Figure 1 (the PE sublayer is enlarged). [Figure 4] FIG. 4 is a schematic diagram of how microlayers can be created in a feedblock by layer multiplication in a coextrusion process. [Figure 5] FIG. 5 is a schematic diagram of how microlayers can be created by layer splitting in a coextrusion process. [Figure 6] FIG. 6 is a cross-sectional scanning electron micrograph (SEM) at 5,000x magnification of an exemplary trilayer or trilayer (having three triple-microlayer sublayers laminated together, for a total of nine microlayers) PP / PE / PP microporous membrane of the present invention (wherein at least the outer PP sublayer is microporous). [Figure 7] Figure 7 is a surface scanning electron micrograph (SEM) at 3,000x magnification of the surface of the polypropylene surface sub-layer (surface PP microlayer) of the nine-microlayer, three-layer membrane of Figure 9. This nine-microlayer membrane can be used, for example, as one layer of the three-layer (9 sublayers, 27 microlayers) membrane shown in Figure 1. [Figure 8]FIG. 8 is a surface scanning electron micrograph (SEM) at 10,000x magnification of a portion of the surface of the polypropylene surface sublayer (surface PP microlayer) of the nine-microlayer trilayer membrane of FIG. [Figure 9] FIG. 9 is a surface scanning electron micrograph (SEM) at 30,000x magnification of a portion of the surface of the polypropylene surface sub-layer (surface PP microlayer) of the nine-microlayer tri-layer membrane of FIG. [Figure 10] Figure 10 is a cross-sectional scanning electron micrograph (SEM) at 5,000x magnification of an exemplary three "microlayer" coextruded sublayer (PO1 / PO2 / PO1) microporous membrane of the present invention, with microlayer PO2 made from a different resin or resin blend than microlayer PO1 to more clearly illustrate the interface (interface zone) of adjacent coextruded microlayers (at least the outer PO1 microlayer is microporous). The multiple coextruded microlayer interfaces and laminated interfaces between adjacent sublayers are believed to impart unique characteristics, properties, and / or performance to the multilayer structure of the present invention. The example sublayer in Figure 13 is made from three layers of PP, with the central PP layer made from a different PP resin than the outer two layers, and had to be run with a thicker precursor due to the lower viscosity of the central PP layer (typically, the microlayers are each less than 4 um, preferably less than 3 um, and more preferably less than 2 um). [Figure 11] FIG. 11 is a markup of a portion of the SEM of FIG. 13 showing the interfacial region with red and green horizontal lines. [Figure 12] FIG. 12 is an enlarged version of FIG. 13 showing the unique pore and membrane structure. [Figure 13]Figure 13 is a schematic representation of an exemplary 12 μm, three-layer membrane according to at least one embodiment of the present invention (each of the sublayers is a different, co-laminated PP / PE / PP sublayer or microlayer; the top PP sublayer has three coextruded PP microlayers; the middle PE sublayer has three PE microlayers that may be the same or different from each other; and the bottom PP sublayer has two PP blend microlayers and one PP microlayer). Figure 16 illustrates that many different embodiments are possible in a single, nine-microlayer membrane, and that variations in the sublayers and individual microlayers are possible and sometimes desirable. For example, one may want to add some PE in the outermost PP microlayer to increase adhesion, wettability, lamination bond strength, etc. [Figure 14] Figure 14 is a schematic representation of an exemplary 3, 9, 18, or 21 microlayer embodiment or example according to the present invention (blue represents PP microlayers, yellow represents PE microlayers, and numbered black lines indicate interfaces). Figure 14 illustrates that many different embodiments are possible and that variations in the use of PP or PE sublayers are possible and sometimes desirable. For example, one may want to add some PE in the outer or center sublayers to increase adhesion, wettability, lamination bond strength, or to provide center shutdown functionality, etc. [Figure 15] FIG. 15 lists a number of non-limiting exemplary embodiments, features, advantages, or configurations of the present multi-layer products and concepts. [Figure 16]16 is a cross-sectional SEM at 10,000X showing nine microlayer (each sublayer has three microlayers) PP / PE / PP sublayers for a -14 um film with a central PE sublayer about 3.11 um thick (each with individual PE microlayers only about 1.037 um thick). The present invention can be used to create multi-microlayer structures from polyolefin resins with excellent performance into other PO films with microlayers each 2 um or less, with microlayers each 1.5 um or less, with microlayers each 1.3 um or less, with microlayers each 1.15 um or less, with microlayers each 1.05 um or less, etc. [Figure 17] FIG. 17 includes an SEM image of a polypropylene layer of a multi-layer product according to some embodiments described herein. [Figure 18] FIG. 18 contains an SEM image of the polypropylene layer of a more conventional three-layer product described herein. [Figure 19] FIG. 19 includes an SEM image of a polyethylene layer of a multi-layer product according to some embodiments described herein. [Figure 20] FIG. 20 contains an SEM image of the polyethylene layer of a more conventional three-layer product described herein. [Figure 21] FIG. 21 contains SEM images showing a side-by-side comparison of the polypropylene layers of the three-layer and multi-layer products described herein. [Figure 22] FIG. 22 contains SEM images showing a side-by-side comparison of the polyethylene layers of the three-layer and multi-layer products described herein. [Figure 23] FIG. 23 includes SEM images showing a side-by-side comparison of the three-layer or multi-layer products described herein. [Figure 24] FIG. 24 is a schematic diagram of the machine learning test. [Figure 25] FIG. 25 shows the coefficients and boundary parameters (PP) from the machine learning experiments described herein. [Figure 26]FIG. 26 shows the coefficients and boundary parameters (PE) from the machine learning experiments described herein. [Figure 27] FIG. 27 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 28] FIG. 28 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 29] FIG. 29 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 30] FIG. 30 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 31] FIG. 31 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 32] FIG. 32 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 33] FIG. 33 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 34] FIG. 34 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 35] FIG. 35 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 36] FIG. 36 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 37] FIG. 37 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 38] FIG. 38 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 39] FIG. 39 is a schematic representation of certain coextruded multilayer precursors, membranes or separators according to some additional embodiments described herein. [Figure 40] FIG. 40 is a graph showing an overlay of storage modulus (E") and loss modulus (E') for a multi-layer microporous membrane and for a three-layer microporous membrane according to some embodiments described herein. [Figure 41] FIG. 41 is a graph showing a where log10a is the tangent(delta) over a temperature range of -140°C to 170°C for a multi-layer microporous membrane and for a three-layer microporous membrane according to some embodiments described herein, and FIG. 52b is a graph showing the tangent(delta) over a temperature range of -140°C to 170°C. [Figure 42] FIG. 42 is a graph showing the offset storage modulus (E") and loss modulus (E') for a multi-layer microporous membrane and for a three-layer microporous membrane according to some embodiments described herein. [Figure 43] FIG. 43 is a graph showing offset tangent (delta) for a multi-layer microporous membrane and for a three-layer microporous membrane according to some embodiments described herein. [Figure 44] FIG. 44 shows peak analysis for a multi-layer microporous membrane and for a three-layer microporous membrane according to some embodiments described herein. [Figure 45] FIG. 45 is a graph showing the storage modulus (E"), loss modulus (E'), and tangent (delta) for three-layer microporous membranes at temperatures from -100°C to 150°C. [Figure 46] FIG. 46 is a graph showing the storage modulus (E"), loss modulus (E'), and tangent (delta) at temperatures from -100°C to 150°C for multilayer microporous membranes according to some embodiments described herein. [Figure 47] FIG. 47 is a graph showing the storage modulus (E"), loss modulus (E'), and tangent (delta) at temperatures from -100°C to 150°C for multi-layer microporous membranes according to some embodiments described herein. [Figure 48] FIG. 48 is a graph showing the storage modulus (E"), loss modulus (E'), and tangent (delta) at temperatures from -100°C to 150°C for multilayer microporous membranes according to some embodiments described herein. [Figure 49] FIG. 49 is a graph showing compressibility data for multi-layer and tri-layer microporous membranes according to certain embodiments described herein. [Figure 50] FIG. 50 is a table containing compressibility data for multi-layer and tri-layer microporous membranes according to some embodiments described herein. [Figure 51] FIG. 51 is a table containing elongation at break data for the multi-layer and three-layer embodiments described herein. [Figure 52] FIG. 52 is a table containing high temperature shrinkage data at 120° C. for the multi-layer and three-layer embodiments described herein. [Figure 53] FIG. 53 is a schematic diagram of a multi-layer microporous membrane according to some embodiments described herein. [Figure 54] 54 is a schematic diagram illustrating the formation of a multi-layer microporous membrane according to some embodiments described herein. The formed multi-layer microporous membrane is on the right side of the figure. [Figure 55] 55 is a schematic diagram illustrating the formation of a multi-layer microporous membrane according to some embodiments described herein. The formed multi-layer microporous membrane is on the right side of the figure. [Figure 56]56 is a schematic diagram illustrating the formation of a multi-layer microporous membrane according to some embodiments described herein. The formed multi-layer microporous membrane is on the right side of the figure. [Figure 57] 57 is a schematic diagram illustrating the formation of a multi-layer microporous membrane according to some embodiments described herein. The formed multi-layer microporous membrane is on the right side of the figure. [Figure 58] FIG. 58 is a schematic diagram of a multi-layer microporous membrane according to some embodiments described herein. [Figure 59] 59 is a schematic diagram illustrating the formation of a multi-layer microporous membrane according to some embodiments described herein. The formed multi-layer microporous membrane is on the right side of the figure. [Figure 60] FIG. 60 is a schematic diagram of a multi-layer microporous membrane according to some embodiments described herein. [Figure 61] FIG. 61 is a table containing data for a control sample without a polymer additive and samples in which the amount and type of functional polymer was varied according to some embodiments described herein. [Figure 62] FIG. 62 is a table containing data for a control sample without a polymer additive and samples in which the amount and type of functional polymer was varied according to some embodiments described herein. [Figure 63] FIG. 63 includes SEM images (5,000x) for a control sample without polymer additive and samples with varying amounts and types of functional polymer according to some embodiments described herein. [Figure 64] Figure 64 includes SEM images (20,000x, sides A and B) for a control sample with no polymer additive and samples with varying amounts and types of functional polymer according to some embodiments described herein. [Figure 65]FIG. 65 is a table containing data for a control sample with no additive and for samples with varying amounts and types of additives according to some embodiments described herein. [Figure 66] FIG. 66 is an SEM of a collapsed-cell microporous membrane according to some embodiments described herein. [Figure 67] FIG. 67 is an SEM of a collapsed-cell microporous membrane according to some embodiments described herein. [Figure 68] FIG. 68 is a table containing data collected for several embodiments described herein. [Figure 69] FIG. 69 is a graph containing mean puncture (g) data for several embodiments described herein. [Figure 70] FIG. 70 is a table containing data collected for several embodiments described herein. [Figure 71] FIG. 71 shows the results of a nail penetration test performed on some of the embodiments described herein. DETAILED DESCRIPTION OF THE INVENTION

[0051] The embodiments described herein may be more readily understood by reference to the following detailed description, examples, and figures. However, the elements, devices, and The present invention is not limited to the specific embodiments set forth in the detailed description, examples, and figures. It is to be understood that these embodiments are merely illustrative of the principles of the invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

[0052] Additionally, all ranges disclosed herein should be understood to encompass any and all subranges subsumed therein. For example, a stated range of "1.0 to 10.0" should be understood to include any and all subranges beginning with a minimum value of 1.0 or greater and ending with a maximum value of 10.0 or less, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0053] All ranges disclosed herein should also be considered to include the endpoints of the range, unless expressly stated otherwise. For example, the range "between 5 and 10," "from 5 to 10," or "5 to 10" should generally be considered to include the endpoints 5 and 10.

[0054] Furthermore, when the phrase "up to" is used in conjunction with an amount or quantity, it should be understood that the amount is at least a detectable amount or quantity. For example, a material present in an amount that is "up to" a particular amount may be present in an amount from a detectable amount up to and including such particular amount.

[0055] Described herein are: microporous multilayer films or membranes; battery separators comprising at least one of the microporous multilayer films or membranes; batteries, particularly lithium ion batteries, comprising at least one of the battery separators described herein, devices comprising the batteries described herein, and methods of making the microporous multilayer films or membranes.

[0056] The multilayer microporous films or membranes exhibit improved properties, particularly when compared to previous three-layer and multilayer microporous films having the same thickness, Gurley, and / or porosity. Improved film or membrane properties include, but are not limited to, improved puncture strength (gf) compared to previous three-layer and multilayer products, improved blend penetration average (N) compared to previous three-layer and multilayer products, improved elongation (kgf / cm) compared to previous three-layer and multilayer products, and improved elongation (kgf / cm) compared to previous three-layer and multilayer products. 2), higher shutdown rates (Ω-cm ) compared to previous three-layer and multilayer products. 2 ), higher average dielectric breakdown (DB) values ​​(V) compared to previous three-layer and multilayer products, lower DB standard deviations (V) compared to previous three-layer and multilayer products, higher minimum DB values ​​(V) compared to previous three-layer and multilayer products, passing industrial nail penetration tests not passed by previous three-layer and multilayer microporous films, improved cycle life, may contain at least one additive in at least one layer, have improved elasticity above 150°C, have improved compressibility, have improved elongation at break (TD), have improved high temperature shrinkage at 150°C, have improved high temperature shrinkage at 120°C, may have at least one polymer blend in at least one layer, and may have nonwoven or woven fabrics attached to one or both sides compared to previous three-layer and multilayer products. The multilayer microporous films herein have also been found to have a unique structure. The unique structure of these films explains many of the improved properties observed.

[0057] Battery separator A battery separator herein refers to a (i.e., one or more) multilayer microporous membrane or film, and, optionally, a polymeric ... The film may comprise, consist of, or consist essentially of a coating layer on one side of the film. The film alone, i.e., without the coating or any other additional components, exhibits the improved properties described above. The performance of the film may be further improved by the addition of a coating or other additional components.

[0058] (1) Multilayer microporous film or membrane In some embodiments, the multilayer membrane or multilayer microporous film comprises 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 11 or more, 12 or more, 13 or more, 14 or more, 15 or more, 15 or more, 16 or more, 17 or more, 18 or more, 19 or more, 20 or more, 21 or more, 22 or more, 23 or more, 24 or more, 25 or more, 26 or more, 27 or more, 28 or more, 29 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more layers. By the term "layer," we mean including a monoextruded layer having a thickness of 2 to 20 microns. As will be understood by those skilled in the art, a monoextruded layer is a layer extruded alone, without any other layers. Additionally, layers of coextruded bi-layer, tri-layer, or multi-layer films are each considered to be "layers" for purposes of determining whether a given battery separator is a multilayer battery separator. The number of layers in a coextruded two-layer film is two, the number of layers in a coextruded three-layer film is three, and the number of layers in a coextruded multilayer film is two or more, preferably three or more, or four or more. The exact number of layers in a two-layer, three-layer, or multilayer coextruded film is determined by the die design and, although not necessarily, the materials being coextruded to form the coextruded film. For example, a coextruded two-, three-, or multilayer film may be formed using the same materials to form two, three, four, or more layers, which are still separate layers even though each is made from the same material. The exact number is likewise determined by the die design. The layers of the coextruded, two-, three-, or multi-layer film each have a thickness of 0.01 to 20 microns, preferably 0.1 to 5 microns, and most preferably 0.1 to 3 microns, 0.1 to 2 microns, 0.1 to 1 micron, 0.01 to 0.8 microns, 0.01 to 0.9 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 microlayers.

[0059] In some embodiments, the multilayer microporous films or membranes disclosed herein comprise 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, consecutive coextruded layers may be formed by the same or different coextrusion processes. For example, at least two or at least three consecutive layers may be formed by the same coextrusion process, or two or more layers may be coextruded by one process, and two or more layers may be coextruded by different processes, or two or more layers formed by one process may be laminated to two or more layers formed by different processes that are combined to form four or more consecutive 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-five or more, forty or more, forty-five or more, fifty-five 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 two or more polymer mixtures, which may be the same or different, with or without a solvent. A preferred coextrusion process is a solvent-free dry process, such as the Celgard® dry process.

[0060] In some embodiments, the multilayer microporous films described herein or Multilayer films are made by forming a coextruded bilayer (two coextruded layers), trilayer (three coextruded layers), or multilayer (two or more, preferably three or more or four or more coextruded layers) film and then laminating the bilayer, trilayer, or multilayer film to at least one, but preferably sometimes two, other films. The at least one, but preferably sometimes two, other films may be nonwoven or woven films, monoextruded films, or coextruded films. In a preferred embodiment, the other films are coextruded films having the same number of coextruded layers as the coextruded bilayer, trilayer, or multilayer film. For example, when a coextruded trilayer film is formed, the other layers are also coextruded trilayers.

[0061] Lamination of a two-layer, three-layer, or multi-layer coextruded film with at least one other monoextruded monolayer film or two-layer, three-layer, or multi-layer film can involve the use of heat, pressure, or preferably heat and pressure.

[0062] In some embodiments, the coextrusion and lamination steps can be part of a bubble or blown film extrusion process. In such processes, two or more polymers, which may be the same or different, are coextruded to form bubbles, and lamination occurs when the bubbles collapse in on themselves. Disintegration devices include roller disintegration devices (including spreader rollers, nip rollers, and segmented rollers) and air disintegration devices.

[0063] Polymers or copolymers that can be used in current battery separators are those that are extrudable. Such polymers are typically referred to as thermoplastic polymers.

[0064] In some embodiments, one or more of the layers of the multilayer microporous film or membrane comprises a polymer or copolymer, or a polymer or copolymer blend, preferably a polyolefin or polyolefin blend. As understood by those skilled in the art, a polyolefin blend may comprise two or more different types of polyolefins, such as a mixture of polyethylene and polypropylene, a blend of two or more of the same type of polyolefins, each with different properties, such as an ultra-high molecular weight polyolefin and a low or ultra-low molecular weight polyolefin, or a mixture of a polyolefin and another type of polymer or copolymer or optional additives.

[0065] Polyolefins include, but are not limited to, polyethylene, polypropylene, polybutylene, polymethylpentene, copolymers thereof, and blends thereof. In some embodiments, the polyolefin can be an ultra-low molecular weight, low molecular weight, medium molecular weight, high molecular weight, or ultra-high molecular weight polyolefin, such as medium or high molecular weight polyethylene (PE) or polypropylene (PP). For example, ultra-high molecular weight polyolefins can have a molecular weight of 450,000 (450k) or more, e.g., 500k or more, 650k or more, 700k or more, 800k or more, 1,000,000 or more, 2,000,000 or more, 3,000,000 or more, 4,000,000 or more, 5,000,000 or more, 6,000,000 or more, etc. High molecular weight polyolefins can have a molecular weight in the range of 250k to 450k, e.g., 250k to 400k, 250k to 350k, or 250k to 300k. The medium molecular weight polyolefin may have a molecular weight of 150 to 250 kJ, e.g., 100 kJ, 125 kJ, 130 kJ, 140 kJ, 150 kJ to 225 kJ, 150 kJ to 200 kJ, or 150 kJ to 200 kJ. The low molecular weight polyolefin may have a molecular weight in the range of 100 kJ to 150 kJ, e.g., 100 kJ to 125 kJ. The ultra-low molecular weight polyolefin may have a molecular weight of less than 100 kJ. The above values ​​are weight average molecular weights. In some embodiments, higher molecular weight polyolefins may be used to increase the strength or other properties of the microporous multilayer membranes described herein or batteries including the same. In some embodiments, lower molecular weight polymers, e.g., medium, low, or ultra-low molecular weight polymers, may be used. For example, without wishing to be bound by any particular theory, it is believed that the crystallization behavior of lower molecular weight polyolefins can result in microporous multilayer films with smaller pores resulting from at least the MD stretching process that forms the pores.

[0066] Exemplary thermoplastic polymers, blends, mixtures, or copolymers other than polyolefin polymers, blends, or mixtures include, but are not limited to, polyacetal (or polyoxymethylene), polyamides, polyesters, polysulfides, polyvinyl alcohol, polyvinyl esters, and polyvinylidene (and may include PVDF, PVDF:HFP, PTFE, PEO, PVA, PAN, etc.). 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, polyester terephthalate, polybutyl terephthalate, copolymers thereof, and blends thereof. Polysulfides include, but are not limited to, polyphenyl sulfide, copolymers thereof, and blends thereof. Polyvinyl alcohols include, but are 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. Polyvinylidenes include, but are not limited to: fluorinated polyvinylidenes (e.g., polyvinylidene chloride, polyvinylidene fluoride), their copolymers, and blends thereof. Various materials may be added to such polymers. These materials are added to modify or enhance the performance or properties of individual layers or the separator as a whole. Such materials include, but are not limited to, materials that lower the melting temperature of the polymer. Typically, multilayer separators contain layers designed to close their pores at a predetermined temperature, thereby blocking the flow of ions between the battery's electrodes. This function is commonly referred to as shutdown.

[0067] In some embodiments, each layer of a multilayer microporous film or membrane comprises, consists of, or consists essentially of a different polymer or copolymer or polymer or copolymer blend. In some embodiments, each layer comprises, consists of, or consists essentially of the same polymer or copolymer or polymer or copolymer blend. In some embodiments, alternating layers of a multilayer microporous film or membrane comprise, consist of, or consist essentially of the same polymer or copolymer or polymer or copolymer blend. In other embodiments, some of the layers of a multilayer film or microporous multilayer film comprise, consist of, or consist essentially of, and some do not, the same polymer or polymer blend.

[0068] While it may be preferred that each of the above layers or microlayers comprise, consist of, or consist essentially of a polyolefin (PO), e.g., PP or PE, or PE+PP blends, mixtures, copolymers, etc., it is contemplated that other polymers (PY), additives, agents, materials, fillers, and / or particles (M), etc., may be added or used to form layers or microlayers, e.g., 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, etc. thereof.

[0069] Also, the same, similar, different, or different PP or PE or PE+PP polymers, homopolymers, copolymers, molecular weights, blends, mixtures, copolymers, etc. may be used. For example, the same, similar, different, or different molecular weight PP, PE, and / or PP+PE polymers, homopolymers, copolymers, multipolymers, blends, mixtures, copolymers, etc. Blends, etc. may be used in each layer, so that configurations may include various combinations and subcombinations 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 configurations.

[0070] In some embodiments, one or more additives may be added to the outermost layer of a multilayer microporous film or membrane to improve its properties or the properties of a battery separator or battery containing the same. The outermost layer may comprise PE, PP, or PE+PP in addition to the additive. For example, additives such as lithium stearate, calcium stearate, PE beads, siloxanes, and polysiloxanes may be added to improve pin removal (i.e., to reduce the coefficient of friction of the film or membrane).

[0071] Certain polymers, copolymers, or polymer or copolymer blends can also be used in the outermost layers of multilayer microporous films or membranes to improve their properties or the properties of battery separators or batteries containing them. For example, the addition of ultra-high molecular weight polymers or copolymers in the outermost layers can improve puncture strength.

[0072] In a further embodiment, an additive that improves oxidation resistance may be added to the outermost layer of the multilayer microporous film or membrane. The additive may be an organic or inorganic additive, or a polymeric or non-polymeric additive.

[0073] In some embodiments, the outermost layer of a multilayer film or membrane may comprise, consist of, or consist essentially of polyethylene, polypropylene, or a mixture thereof.

[0074] In some embodiments, a microporous multilayer film or membrane may include three or more distinct regions or sub-membrane areas. In preferred embodiments, one or more of the regions or sub-membrane areas may comprise, consist of, or consist essentially of two or more layers, which may or may not be coextruded layers. In some preferred embodiments, two or more layers are coextruded layers. In some embodiments, a laminate barrier exists between a region or sub-membrane area and an adjacent region or sub-membrane area. A laminate barrier is formed when two surfaces, for example, two surfaces of different films or layers, are laminated together using heat, pressure, but preferably heat and pressure. In some embodiments, the sub-membrane areas have the following non-limiting configurations: PP, PE, PP / PP, PP / PE, PE / PP, PE / PE, PP / PP / PP, PP / PP / PE, PP / PE / PE.PP / PE / PP, PE / PP / PE, PE / PE / PP, PP / PP / PP / PP, PP / PE / PE / P P, PE / PP / PP / PE, PP / PE / PP / PP, PE / PE / PP / PP, PE / PP / PE / PP, PP / PE / 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, PE / 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 / PE, 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, PP / 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 / P EPE / 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, PP / PP / PP / PP / PP / PE / PE / PE / PE / PE, PE / PE / PE / PE / PE / PP / PP / PP / PP / PP , PP / PE / PP / PP / PP / PP / PP / PP / PE / PP, PE / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP, PE / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP, PE / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP, PP / PP / PE / PE / PE / PE / PE / PE / PE / PE / PE / PE / PP, PP / PP / PE / PP / PP / PP / PP / PP / PP / PP / PP / PP, PE / PE / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP, PP / PP / PP / PP / PP / PP / PP / PP / PP / PP / PP / PE, PP / PP / PP / PP / PP / PP / PP / PP / PP / PP / PE, PE / PE / PP / PP / PP / PP / PP / PP / PE / PE / PP / PP / PP; As used herein, PE refers to a layer or microlayer, e.g., a coextrusion layer or microlayer, of a region or sub-membrane area that comprises, consists of, or consists essentially of PE. As used herein, PP refers to layers or microlayers, e.g., coextruded layers or microlayers, of a region or sub-membrane area that comprise, consist of, or consist essentially of PP. The PE or PP in different layers or microlayers may be the same or different. Similar variations, including up to 50 layers or microlayers, especially coextruded layers or microlayers, per region or sub-membrane area, can be formed by a suitable extrusion die.

[0075] In one preferred embodiment, the coextruded precursor may have the structure (PP1 / PP2 / PP3)(PP3 / PP2 / PP1), (PP3 / PP3 / PP2 / PP1 / PP1), (PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP2 / PP1 / PP1 / PP1), etc.

[0076] PP1 is made from homopolymer PP and additives that modify the surface coefficient of friction, including optional anti-slip or anti-block additives such as polysiloxanes or siloxanes. PP2 may be made from the same or different PP homopolymer as PP1 and a copolymer of PP. The PP copolymer may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 may be made from the same or different homopolymer PP as PP1 and PP2 and also includes additives that modify the surface coefficient of friction, which may be the same or different from those used in PP1.

[0077] In other preferred embodiments, the coextruded precursor may have the structure (PP1 / PP2 / PP3)(PP3 / PP2 / PP1), (PP3 / PP3 / PP2 / PP1 / PP1), (PP3 / PP3 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP2 / PP1 / PP1), (PP3 / PP3 / PP3 / PP2 / PP2 / PP1 / PP1 / PP1), etc. PP1 may be any polypropylene blend. PP2 may be made from any PP block copolymer, including those described herein. PP3 may be made from the same or a different PP-block copolymer as used in PP2.

[0078] The regions or sub-membrane areas may be arranged in any order to form a microporous multilayer membrane or film. For example, the microporous multilayer membrane or film may have the following non-limiting configurations: (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 / (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); may be included. The above variants can be used to form a microporous multilayer film or multilayer membrane 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 micro-layers.

[0079] The thickness of the microporous multilayer film or membrane is not particularly 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 coatings or treatments are applied.

[0080] Microporous, as used herein, means that the film, membrane, or coating has an average pore size of 2 microns or less, preferably 1 micron or less, 0.9 microns or less, 0.8 microns or less, 0.7 microns or less, 0.6 microns or less, 0.5 microns or less, 0.4 microns or less, 0.3 microns or less, 0.2 microns or less, preferably 0.1 microns or less, 0.09 microns or less, 0.08 microns or less, 0.07 microns or less, 0.06 microns or less, 0.05 microns or less, 0.04 microns or less, 0.03 microns or less, 0.02 microns or less, or 0.01 microns or less. In a preferred embodiment, the pores may be formed, for example, by performing a stretching process on the precursor film, as is done, for example, in the Celgard® dry process.

[0081] In some preferred embodiments, the multilayer microporous film or membrane includes sub-membranes or regions comprising, consisting of, or consisting essentially of PE and is microporous, having an average pore size between 0.03 and 0.1, preferably between 0.05 and 0.09, 0.05 and 0.08, 0.05 and 0.07, or 0.05 and 0.06.

[0082] In other preferred embodiments, the multilayer microporous film or membrane includes sub-membranes or regions comprising, consisting of, or consisting essentially of PP, and is microporous and 0. The average pore diameter is between 0.02 and 0.06, preferably between 0.03 and 0.05, and more preferably between 0.04 and 0.05 or between 0.03 and 0.04.

[0083] In some other preferred embodiments, the multilayer microporous film or membrane comprises sub-membranes or regions comprising, consisting of, or consisting essentially of PP and sub-membranes or regions comprising, consisting of, or consisting essentially of PE, wherein the PP sub-membranes or regions have a smaller average pore size than the PE sub-membranes or regions.

[0084] The Gurley of the microporous multilayer film or membrane is not particularly limited and may have any Gurley that makes it acceptable for use as a battery separator. In some embodiments, the microporous multilayer films or membranes described herein have a JIS Gurley (s / 100cc) of 150 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.

[0085] The porosity of the microporous multilayer film is not particularly limited. 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 10-60%, 20-60%, 30-60%, or 40-60%.

[0086] The microporous multilayer film or membrane, when uncoated, may have a puncture strength of 290 gf or greater, 300 gf or greater, 310 gf or greater, 320 gf or greater, 330 gf or greater, 340 gf or greater, 350 gf or greater, or as high as 400 gf or greater.

[0087] In some embodiments, the multilayer microporous membranes described herein may include one or more additives in at least one layer of the multilayer microporous membrane. In some embodiments, at least one layer of the multilayer microporous membrane includes more than one additive, e.g., two, three, four, five, or more additives. The additive may be present in one or both of the outermost layers of the multilayer microporous membrane, in one or more inner layers, in all of the inner layers, or inside the outermost layer and all of the inner layers. In some embodiments, the additive may be present in one or more outermost layers and one or more innermost layers. In such embodiments, over time, the additive may be released from the outermost layer(s), and the supply of additive in the outermost layer(s) may be replenished by migration of additive in the inner layers to the outermost layer(s). In some embodiments, each layer of the multilayer microporous membrane may include a different additive or combination of additives than the layer or adjacent layers of the multilayer microporous membrane.

[0088] In some embodiments, the additive is, comprises, consists of, or consists essentially of a functional polymer. As understood by those skilled in the art, a functional polymer is a polymer having functional groups detached from the polymer backbone. Exemplary functional groups include: In some embodiments, the functional polymer is a maleic anhydride functional polymer. In some embodiments, the maleic anhydride modified polymer is maleic anhydride homopolymer polypropylene, copolymer polypropylene, high density polypropylene, low density polypropylene, very high density polypropylene, very low density polypropylene, homopolymer polyethylene, copolymer polyethylene, high density polyethylene, low density polyethylene, very high density polyethylene, or very low density polyethylene.

[0089] In some embodiments, the additive comprises, consists of, or consists essentially of an ionomer. An ionomer, as understood by those skilled in the art, is a copolymer that contains both ionic and nonionic repeating groups. The ion-containing repeat groups may comprise less than 25%, less than 20%, or less than 15% of the ionomer. In some embodiments, the ionomer may be a Li-based, Na-based, or Zn-based ionomer.

[0090] In some embodiments, the additive comprises cellulose nanofibers.

[0091] In some embodiments, the additive comprises inorganic particles having a narrow size distribution. For example, the difference between D10 and D90 in the distribution is less than 100 nanometers, less than 90 nanometers, less than 80 nanometers, less than 70 nanometers, less than 60 nanometers, less than 50 nanometers, less than 40 nanometers, less than 30 nanometers, less than 20 nanometers, or less than 10 nanometers. In some embodiments, the inorganic particles are selected from at least one of SiO2, TiO2, or a combination thereof.

[0092] In some embodiments, the additive may comprise, consist of, or consist essentially of a lubricant. The lubricants or lubricating oils described herein are not so limited. As understood by those skilled in the art, lubricants are compounds that act to reduce friction between a variety of different surfaces, including the following: polymer:polymer; polymer:metal; polymer; organic materials; and polymer:inorganic materials. Specific examples of lubricants or lubricating oils described herein are compounds containing siloxy functional groups, including siloxanes and polysiloxanes, and fatty acid salts, including metal stearates.

[0093] Compounds containing two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more siloxy groups may be used as lubricants as described herein. Siloxanes, as understood by those skilled in the art, are a class of molecules having a backbone of alternating silicon (Si) and oxygen (O) atoms, each of which may have an attached hydrogen (H) or saturated or unsaturated organic group, such as —CH3 or —CH5. Polysiloxanes are polymerized siloxanes, typically having higher molecular weights. In some preferred embodiments described herein, the polysiloxanes may be high molecular weight, or even more preferably, in some cases, ultra-high molecular weight polysiloxanes. In some embodiments, high and ultra-high molecular weight polysiloxanes may have a weight average molecular weight ranging from 500,000 to 1,000,000.

[0094] The fatty acid salts described herein are also not particularly limited and may be any fatty acid salt that functions as a lubricant. The fatty acid of the fatty acid salt may be a fatty acid having 12 to 22 carbon atoms. For example, the metal fatty acid may be selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, behenic acid, erucic acid, and arachidic acid. The metal is not particularly limited, but in preferred embodiments, it is an alkali or alkaline earth metal, such as Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, and Ra. In some preferred embodiments, the metal is Li, Be, Na, Mg, K, or Ca.

[0095] In some preferred embodiments, the fatty acid salt is lithium stearate, sodium stearate, lithium oleate, sodium oleate, sodium palmitate, lithium palmitate, potassium stearate, or potassium oleate.

[0096] In some preferred embodiments described herein, the lubricating oils containing the fatty acid salts described herein have a melting point of 200° C. or higher, 210° C. or higher, 220° C. or higher, 230° C. or higher, or 240° C. or higher. The fatty acid salts, such as lithium stearate, (melting point of 220°C) or sodium stearate (melting point 245-255°C) have such melting points. Fatty acid salts, such as calcium stearate (melting point 155°C), do not. The inventors of this application have found that calcium stearate is less ideal from a processing standpoint than other fatty acid metal salts, such as metal stearates, which have higher melting points. In particular, they have found that calcium stearate cannot be added in amounts greater than 800 ppm without causing what is known as the "dusting effect," in which wax separates and becomes ubiquitous during the hot extrusion process. While not wishing to be bound by any particular theory, the use of fatty acid metal salts with melting points above the hot extrusion temperature is believed to solve this "dusting" problem. Fatty acid salts with melting points higher than calcium stearate, particularly those with melting points greater than 200°C, can be incorporated in amounts of 1% or greater than 1,000 ppm without causing "dusting." Amounts of 1% or greater have been found to be important to achieve desired properties, such as improved wetting and improved pin removal.

[0097] In some embodiments, the additive may comprise, consist of, or consist essentially of one or more nucleating agents. As will be understood by those skilled in the art, a nucleating agent is a material, preferably an inorganic material, that in some embodiments assists, increases, or enhances the crystallization of polymers, including semi-crystalline polymers.

[0098] In some embodiments, the additive may comprise, consist of, or consist essentially of a cavitation promoting agent, which is a material that forms, assists, increases, or enhances the formation of bubbles or cavities in a polymer, as understood by those skilled in the art.

[0099] In some embodiments, the additive may comprise, consist of, or consist essentially of a fluoropolymer, which is not so limited and in some embodiments is PVDF.

[0100] In some embodiments, the additive may comprise, consist of, or consist essentially of a crosslinking agent.

[0101] In some embodiments, the additive may comprise, consist of, or consist essentially of an x-ray detectable material. The x-ray detectable material is not so limited and may be any material, such as those disclosed in U.S. Patent No. 7,662,510, which is incorporated herein by reference in its entirety. Suitable amounts of x-ray detectable materials or elements are also disclosed in the '510 patent, but in some embodiments, In some preferred embodiments, the additive is barium sulfate.

[0102] In some embodiments, the additive may comprise, consist of, or consist essentially of a lithium halide. The lithium halide may be lithium chloride, lithium fluoride, lithium bromide, or lithium iodide. In some preferred embodiments, the lithium halide may be lithium iodide, which is both ionically conductive and electronically insulating. Materials that are both ionically conductive and electronically insulating are particularly preferred for use as part of a battery separator.

[0103] In some embodiments, the additive may include, consist of, or consist essentially of a polymer processing agent. As such, polymer processing agents or additives are added to improve the processing efficiency and quality of polymer compounds. In some embodiments, the polymer processing agent may be an antioxidant, stabilizer, lubricant, processing aid, nucleating agent, colorant, antistatic agent, plasticizer, or filler.

[0104] In some embodiments, the additive may comprise, consist of, or consist essentially of a high temperature melt index (HTMI) polymer, which is not so limited and may be at least one selected from the group consisting of PMP, PMMA, PET, PVDF, aramid, syndiotactic polystyrene, and combinations thereof.

[0105] In some embodiments, the additive may comprise, consist of, or consist essentially of an electrolyte additive. 1The electrolyte additives described herein are not particularly limited, so long as the electrolyte meets the goals described herein. The electrolyte additive may be any additive typically added by battery manufacturers, particularly lithium battery manufacturers, to improve battery performance. The electrolyte additive may also be combined with the polymer used in the polymeric microporous film, e.g., must be miscible with the polymer or compatible with the coating slurry. The compatibility of the additive may also be supplemented or improved by coating or partially coating the additive. For example, exemplary electrolyte additives are described in "A Review of Electrolyte Additives for Lithium-Ion Batteries," J. of Power Sources, vol. 162, issue 2, 2006, pp. 1379-1394, the entire contents of which are incorporated herein by reference. In some preferred embodiments, the electrolyte additive is at least one selected from the group consisting of an SEI improver, a cathode protectant, a flame retardant additive, a LiPF salt stabilizer, an overcharge protectant, an aluminum corrosion inhibitor, a lithium precipitation agent or improver, or a solvation promoter, an aluminum corrosion inhibitor, a wetting agent, and a thickener. In some embodiments, the additive may have more than one property, for example, it may be a wetting agent and a thickener.

[0106] Exemplary SEI improvers include VEC (vinyl ethylene carbonate), VC (vinylene carbonate), FEC (fluoroethylene carbonate), and LiBOB (lithium bis(oxalato)borate). Exemplary cathodic protectants include N,N'- Examples of suitable flame retardant additives include dicyclohexylcarbodiimide, N,N-diethylaminotrimethylsilane, and LiBOB. Exemplary flame retardant additives include TTFP (tris(2,2,2-trifluoroethyl)phosphate), fluorinated propylene carbonate, and MFE (methyl nonafluorobutyl ether). Exemplary LiPF6 salt stabilizers include LiF, TTFP (tris(2,2,2-trifluoroethyl)phosphite), 1-methyl-2-pyrrolidinone, fluorinated carbamates, and hexamethylphosphoramide. Exemplary overcharge protection agents include xylene, cyclohexylbenzene, biphenyl, 2,2-diphenylpropane, and phenyl-tert-butyl carbonate. Exemplary Li deposition improvers include AlI3, SnI2, cetyltrimethylammonium chloride, perfluoropolyethers, and tetraalkylammonium chlorides with long alkyl chains. Exemplary ion salvation enhancers include 12-crown-4, TFPPB (tris(pentafluorophenyl)). Exemplary Al corrosion inhibitors include LiBOB, LiODFB, e.g., borate salts. Exemplary wetting agents and viscosity reducers include cyclohexane and PO.

[0107] In some preferred embodiments, the electrolyte additive is air stable or oxidation resistant. Battery separators containing the electrolyte additives disclosed herein may last for several weeks. The battery separator may have a shelf life of up to several months, e.g., 1 week to 11 months. This means that, for example, at 1 week, 2 weeks, 3 weeks, 4 weeks, 2 months, 3 months, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months, or 11 months, the separator retains its ability to release electrolyte additives into the electrolyte of a lithium-ion battery when the battery separator is used in the lithium-ion battery. For example, it retains 70%, 80%, 90%, 95%, or 100% of its original ability to release electrolyte additives into the electrolyte of a lithium-ion battery. Once incorporated into a battery, the battery separator is no longer exposed to air and is therefore no longer affected by oxidation to any significant extent. This shelf life is measured without the addition of a coating to prevent or retard oxidation, although a coating may be added to the separator to prevent oxidation and extend the shelf life of the battery separator.

[0108] In some embodiments, the additive may comprise, consist of, or consist essentially of an energy-dissipating immiscible additive, where immiscible means that the additive is not miscible with the polymers used to form the layers of the multi-layer microporous membrane or film containing the additive.

[0109] In some embodiments, the membranes or films described herein have or exhibit increased or improved elasticity at 150°C or higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multilayer microporous membrane or film. In some embodiments, the increased or improved elasticity can be measured using dynamic mechanical analysis as described herein. In some embodiments, the tangent (delta) of the multilayer membranes or films described herein is greater than -0.6 at 150°C as measured by dynamic mechanical analysis. In some embodiments, the tangent (delta) of the multilayer membranes or films described herein is between -1.0 and -0.6 at temperatures between 175°C and 200°C as measured by dynamic mechanical analysis. In some embodiments, the tangent (delta) of the multilayer membranes or films described herein is between -0.9 and -0.6, between -0.8 and -0.6, or between -0.7 and -0.6 at temperatures between 175°C and 200°C as measured by dynamic mechanical analysis. In some embodiments, the tangent (delta) of the multilayer microporous membranes or films described herein is greater than -1.2, greater than -1.1, greater than -1.0, greater than -0.9, or greater than -0.8 at temperatures of 200°C or greater.

[0110] In some embodiments, the membranes or films described herein have or exhibit increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin composition as the multi-layer microporous membrane or film. In some embodiments, the percent recovery, as measured by the compression recovery method described herein, is greater than 9%, greater than 9.1%, greater than 9.2%, greater than 9.3%, greater than 9.4%, greater than 9.5%, greater than 9.6%, greater than 9.7%, greater than 9.8%, greater than 9.9%, greater than 10.0%, greater than 10.1%, greater than 10.2%, greater than 10.3%, greater than 10.4%, or greater than 10.5%. Sometimes, the percent recovery can be as high as 15% or 20%.

[0111] In some embodiments, the multilayer microporous membranes or films described herein exhibit increased or improved elongation at break (TD) compared to a three-layer microporous membrane or film having the same thickness, Gurley, porosity, and / or resin configuration as the multilayer microporous membrane or film. In some embodiments, the elongation at break is greater than 30% higher, greater than 31% higher, greater than 32% higher, greater than 33% higher, greater than 34% higher, greater than 35% higher, greater than 36% higher, greater than 37% higher, greater than 38% higher, greater than 39% higher, greater than 40 ... and high, greater than 41%, greater than 42%, greater than 43%, greater than 44%, greater than 45%, greater than 46%, greater than 47%, greater than 48%, greater than 49%, greater than 50%, greater than 51%, greater than 52%, greater than 53%, greater than 54%, greater than 55%, greater than 56%, greater than 57%, greater than 58%, greater than 59%, or greater than 60%.

[0112] In some embodiments, the multilayer microporous membranes or films described herein have or exhibit reduced high temperature shrinkage at 120° C. compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film. In some embodiments, the membranes or films described herein have or exhibit reduced high temperature shrinkage of 30-75% lower, 30-74% lower, 30-73% lower, 30-72% lower, 30-71% lower, 30-70% lower, 30-69% lower, 30-68% lower, 30-67% lower, 30-66% lower, 30-65% lower, 30-64% lower, 30-63% lower, 30-62% lower, 30-61% lower, 30-60% lower, 30-59% lower, 30-58 ... ~57% lower, 30-56% lower, 30-55% lower, 30-54% lower, 30-53% lower, 30-52% lower, 30-51% lower, 30-50% lower, 30-49% lower, 30-48% lower, 30-47% lower, 30-46% lower, 30-45% lower, 30-44% lower, 30-43% lower, 30-42% lower, 30-41% lower, 30-40% lower, 30-39% lower, 30-38% lower, 30-37% lower, 30-36% lower, 30-35% lower, 30-34%, 30-33% lower, 30-32% lower, or 30-31% lower high temperature shrinkage at 120°C.

[0113] In some embodiments, at least one layer of the multilayer films or films described herein includes a polymer additive. The polymer additive is added in an amount less than the main polymer that constitutes the film. For example, in some embodiments, the main polymer may be a polyolefin. This is another way of saying that at least one layer of the multilayer films or films described herein includes or is composed of a polymer blend. In some embodiments, the layer may include or be composed of one or more of the polymer or polymer blend and other additives described herein.

[0114] In some embodiments, the layer comprising the polymer blend is an outer layer. In some embodiments, both outer or outermost layers comprise the polymer blend. In some embodiments, an inner layer comprises the polymer blend. Sometimes, at least one inner layer and at least one outer layer comprise the polymer blend, and in some embodiments, all of the outer or outermost layers and all of the inner layers comprise the polymer blend.

[0115] In some embodiments, the polymer blend comprises, consists of, or consists essentially of at least two different polyolefins, such as at least two different polyethylenes, at least two different polypropylenes, or a combination of at least one polyethylene and one polypropylene. In some embodiments, the polymer blend comprises, consists of, or consists essentially of a polyolefin and a non-polyolefin, i.e., a polymer that is not a polyolefin.

[0116] In some embodiments, each layer of a multilayer film or membrane has a different composition than the layer adjacent to it. For example, one layer may be a polymer blend of two different polyolefins. One adjacent layer may comprise a polymer blend of polyolefin and non-polyolefin, and the other adjacent one may not comprise a polymer blend.

[0117] In some embodiments, the multilayer membrane or film has a nonwoven or woven fabric attached to one or both sides.

[0118] In some embodiments, a multilayer microporous membrane or film comprises two or more layers and a region in at least one of the layers comprising polyethylene, which region, when tested by the machine learning tests described herein, satisfies the following: w T x' ≥ -2.0, wT x' ≥ -1.0, w T x' ≥ 0.0 or w T x' ≥ 2.0.

[0119] In some embodiments, a multilayer microporous membrane or film comprises two or more layers and a region in at least one of the layers comprising polypropylene, the region satisfying the following when tested by the machine learning tests described herein: T x' ≥ -1.5, w T x' ≥ -1.0, w T x' ≥ 0.5 w T x' ≥ 1.5.

[0120] Regarding the structural characteristics of the microporous multilayer films and membranes described herein, in some embodiments, the tortuosity 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. While not wishing to be bound by any particular theory, it is believed that the observed tortuosity values, particularly values ​​greater than 2.0, 2.1, or 2.2, may be responsible for the increased puncture strength and mixed penetration averages disclosed herein. More flexible films are also believed to be safer when used as battery separators for lithium-ion batteries.

[0121] The MacMullin number of the microporous multilayer films or membranes described herein is 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.

[0122] In some embodiments, the electrical resistivity of the microporous multilayer film or membrane is 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.

[0123] The crystallinity of the microporous multilayer films described herein has been found to differ from that of prior multilayer and three-layer films. For example, in some embodiments where the microporous multilayer film comprises: (1) a first region comprising two or more layers; (2) a second region comprising two or more layers on a first side of the first region; and (3) a third region comprising two or more layers on the opposite side of the first region, at least one of the first, second, or third regions comprises PE and has a lower crystallinity, as measured by DSC, than a PE-containing layer of a three-layer microporous film having the same thickness as the multilayer microporous film. For example, the crystallinity may be 1-20% lower, 1-19%, 1-18%, 1-17%, 1-16%, 1-15% lower, 1-14%, 1-13%, 1-12%, 1-11%, 1-10%, 1-9%, 1-8%, 1-7%, 1-6%, 1-5%, 1-4%, 1-3%, or 1-2% lower than a PE-containing layer of a three-layer microporous film having the same thickness as the multi-layer microporous film.

[0124] Other structural differences between the multilayer microporous films described herein and prior three-layer and multilayer films can be seen using scanning electron microscopy. See, for example, Figures 17-23. For example, as shown in Figures 17-23, a multilayer microporous film or membrane may include at least a first region comprising two or more layers and a second region comprising at least one layer. The first region appears to be largely non-connected when viewed in the z-direction of the film using SEM. The term "majority" means most, but not necessarily all, of the amorphous regions in the first layer, and most, but not necessarily all, of the amorphous regions in the first layer are discontinuous. This can 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. "Discontinuous amorphous regions" means that when a sample of the first layer is analyzed, for example, by SEM, the path of the amorphous regions is interrupted or broken by crystalline (lamellar) regions along the entire thickness of the first layer. Discontinuous means that the path of the amorphous regions is interrupted or broken by crystalline (lamellar) regions along the entire thickness of the first layer. The path of the amorphous regions does not circumnavigate the crystalline (lamellar) regions. Instead, the crystalline (lamellar) regions completely interrupt the path of the amorphous regions along the entire thickness of the first layer. The path of the amorphous regions can be linear or circuitous. An example of the difference between discontinuous and continuous amorphous regions can be seen in Figure 22 by comparing the SEM of the polyethylene layer of COM EX4 with the SEM of the polyethylene layer of Example 6. Discontinuous can also mean that the amorphous regions are non-columnar, non-vertically continuous, or non-pillar-like along the thickness of the layer. In some preferred embodiments, the first region, which is a predominantly discontinuous amorphous region, can comprise, consist of, or consist essentially of polypropylene in some or all of the layers in the region. In some other embodiments, the second region includes two or more layers, and the amorphous areas of the film or membrane region have 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, this can be seen by comparing COM EX4 with Example 6 in Figure 30. 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.

[0125] In some embodiments, the multilayer microporous membranes described herein exhibit an increased puncture average (g) when tested at a higher puncture rate, i.e., a puncture rate greater than 25 mm / min, compared to the puncture average (g) of the same membrane at a puncture rate of 25 mm / min. The puncture average is obtained by taking two puncture force measurements at a given rate and averaging the results. In some embodiments, the higher puncture rate is 100 mm / min, and the puncture average (g) at that rate is at least 20 g, 30 g, 40 g, or 50 g higher than the puncture average (g) at 25 mm / min. The puncture average (g) for the multilayer microporous membranes described herein may be 250 g or greater, 275 g or greater, 300 g or greater, 325 g or greater, or 350 g or greater at a puncture rate of 25 mm / min. In some embodiments, the multilayer membranes that exhibit an increased puncture average (g) when tested at a higher puncture rate have a thickness of 14 to 30 microns.

[0126] (a) Collapsed bubble multilayer microporous membrane The multilayer microporous membrane formed by the collapsed-cell method is not particularly limited. In preferred embodiments, the multilayer microporous membrane formed by the collapsed-cell method is thin. For example, it may have a thickness of 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, less than 5 microns, less than 4 microns, less than 3 microns, or less than 2 microns. In some preferred embodiments, the thickness is between 6 and 12 microns. In some preferred embodiments, the thickness is about 10 microns or between 9 and 11 microns. In addition to being thin, the microporous membrane formed by the collapsed-cell method has a puncture strength of 200 g, 210 g, 220 g, 230 g, or 240 g or greater. In some embodiments, the multilayer microporous membrane formed by the collapsed-cell method may have a Gurley of less than 250, less than 225, less than 200, less than 190, less than 180, or less than 175.

[0127] The structure of the microporous membrane is not so limited, but may have a structure formed by collapsing bubbles, such as microporous membranes formed by collapsing bubbles (or multi-slot dies), or otherwise coextruded PP / PP / PP, PE / PE / PE, PP / PP / PE, PP / PE / PE, PP / PP, PE / PE, PE / PP, PE / PP / PP, PP / PE / PE / PP, PP / PE / PE / PP, PE / PP / PP, PP / PE / PP / PE, PP / PE / PP / PE, PP / PE / PP / PE, and the like. For example, the structure of the final layer or microlayer or nanolayer may be: PP / PE / PE / PP, PP / PP / PP / PP, PE / PE / PE / PE, PE / PP / PP / PE, PP / PP / PE / PE / PP / PP, PP / PE / PE / PE / PE / PP, PP / PE / PE / PE / PE. / PP, PE / PP / PP / PP / PP / PE, PP / PE / PP / PP / PE / PP, PE / PE / PP / PP / PE / PE, PP / PE / PP / PE / PE / PP / PE / PP, PP / PP / PP / PE / PE / PP / PP / PP / PP, PP / PP / PE / PE / PE / PE / PP / PP, etc. For example, structures formed by collapsing cells containing coextruded PP / PE / PE may form layered or microlayered or nanolayered structures such as PP / PE / PE / PE / PE / PP, PP / PP / PE / PE / PE / PE / PE / PP / PP or PP / PE / PE / PE / PE / PE / PE / PE / PP or PP / PP / PP / PE / PE / PE / PE / PE / PP / PP or PP / PE / PE / PE / PE / PE / PE / PE / PE / PP / PP or PP / PE / PE / PE / PE / PE / PE / PE / PE / PP, etc. When more than one PP or PE layer is present in the coextruded cells, the PP layers may be the same or different, and the PE layers may be the same or different (e.g., PP / PP1 / PE / PE2 / PE2 / PE / PP1 / PP).

[0128] Microporous membranes may contain distinct lamination or adhesion interfaces formed when the bubbles collapse (collapse and adhere or stack), which can be seen when a cross-sectional SEM of the membrane is taken. Without wishing to be bound by any particular theory, it is believed that the distinct interfaces arise due to some mismatch that results in the collapse step. Examples of distinct interfaces are shown in Figures 66 and 67.

[0129] In some embodiments, the multilayer microporous membrane formed by the collapsed bubble method comprises polyethylene having a melt flow rate of 0.1 to 10 g / min. The microporous membrane may have at least one layer comprising polyethylene having a thickness of at least 1.75 microns. In some embodiments, the polyethylene-containing layer has a thickness of at least 2 microns. In some embodiments, the polyethylene-containing layer has a thickness of less than 1.75 microns. It is believed that a thickness of at least 2 microns or at least 1.75 microns may be required for shutdown functionality. However, when polyethylenes that result in smaller pores are used, thinner polyethylene-containing layers may be sufficient.

[0130] In some embodiments, the membrane comprises polypropylene having a melt flow rate of 0.01 to 10 g / 10 min, 0.1 to 5 g / 10 min, or 0.01 to 2.5 g / 10 min, as measured by ASTM D1238-13 and / or ISO 1133-1:2011.

[0131] (2) Optional coating In some embodiments, one or more coating layers may be applied to one or two 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, consisting of, or consisting essentially of a polymer binder and organic and / or inorganic particles. In some embodiments, only a ceramic coating is applied to one or both sides of a microporous membrane or film. In other embodiments, A different coating may be applied to the microporous membrane or film before or after application of the ceramic coating. A different additional coating may be applied to one or both sides of the membrane or film. In some embodiments, the different polymer coating layer may comprise, consist of, or consist essentially of at least one of polyvinylidene difluoride (PVdF) or polycarbonate (PC).

[0132] In some embodiments, the thickness of the coating layer is 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.

[0133] The coating method is not particularly limited, and the coating layer described herein can be coated onto the porous substrate by at least one of the following coating methods: extrusion coating, roll coating, gravure coating, printing, knife 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.

[0134] The coating layer may be non-porous, nanoporous, microporous, mesoporous, or macroporous. The coating layer may have a JIS Gurley of 700 or less, sometimes 600 or less, 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0135] One or more layers, treatments, materials, or coatings (CT) and / or nets, meshes, mats, wovens, or nonwovens (NW) may be added to one or both sides of or within the multilayer films or membranes (M) described herein, including, but 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.

[0136] Complex, vehicle, or device A composite comprising the battery separator described hereinabove and one or more electrodes, such as an anode, a cathode, or an anode and a cathode, disposed in direct contact therewith. The type of electrode is not particularly limited. For example, the electrode may be one suitable for use in a lithium-ion secondary battery.

[0137] Suitable anodes may have an energy capacity of 372 mAh / g or greater, preferably ≥ 700 mAh / g, and most preferably ≥ 1000 mAh / g. The anode may be composed of lithium metal foil or lithium alloy foil (e.g., lithium aluminum alloy), or a mixture of lithium metal and / or lithium alloy with materials such as carbon (e.g., coke, graphite), nickel, or copper. The anode is not made solely from a lithium-containing intercalation compound or a lithium-containing insertion compound.

[0138] Suitable cathodes may be any cathode compatible with the anode and may include intercalation compounds, insertion compounds, or electrochemically active polymers. Suitable intercalation materials include, for example, MoS2, FeS2, MnO2, TiS2, NbSe3, LiCoO2, LiNiO2, LiMn2O4, VO 13 , V2O5, and CuCl2. Suitable polymers include, for example, polyacetylene, polypyrrole, polyaniline, and polythiophene.

[0139] Any of the separators described herein above may be incorporated into any vehicle, such as an e-vehicle, or device, such as a fully or partially battery-powered cell phone or laptop.

[0140] Various embodiments of the present invention have been described in order to achieve various objects of the present invention. It is to be understood that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

[0141] fabric In some embodiments, woven fabrics are described that comprise, consist of, or consist essentially of the multilayer microporous membranes or films described herein. In some preferred embodiments, the woven fabric comprises the multilayer microporous membranes or films described herein and a nonwoven or woven material. The nonwoven fabric may be a staple nonwoven, meltblown nonwoven, spunlaid nonwoven, flash-spun nonwoven, airlaid nonwoven, or a nonwoven fabric made by any other process. In some preferred embodiments, the nonwoven or woven fabric is attached to the multilayer microporous membrane or film. In some embodiments, the woven fabric comprises, consists of, or consists essentially of a woven or nonwoven fabric, a multilayer microporous membrane or film described herein, and another woven or nonwoven fabric, in that order. In some embodiments, the woven fabric comprises, consists of, or consists essentially of a multilayer microporous membrane or film described herein, a nonwoven or woven fabric, and a multilayer microporous membrane or film described herein, in that order.

[0142] method The method of forming the multilayer microporous films or membranes described herein is not particularly limited and can be a dry process, preferably the CELGARD® dry stretch process, a dry process such as BNOPP, or a wet process utilizing a solvent or oil.

[0143] The method of forming the multilayer microporous film or membrane described herein includes at least the following steps: (1) co-extruding two or more polymer mixtures, which may be the same or different, to form a co-extruded film, as described herein above, having two or more layers or microlayers; (2) laminating the co-extruded film to at least one other mono-extruded film, co-extruded film, or nonwoven, in which, in some preferred embodiments, the co-extruded film is laminated to two other co-extruded films having two or more microlayers; and (3) optionally, one or more additional steps.

[0144] (1) Co-extrusion step Coextrusion is not so limited. An exemplary coextrusion process is shown in FIG. 4, and a coextrusion die is shown in FIG. 5. In some embodiments, a coextrusion die is used with one or more extruders feeding the die. Typically, there is one extruder for each desired layer or microlayer of the ultimately formed coextruded film. For example, if the desired coextruded film has three microlayers, three extruders are used with the coextrusion die. In at least one embodiment, the inventive film can be comprised of many microlayers or nanolayers, with the final product containing 50 or more individual microlayers or nanolayers. In at least certain embodiments, the microlayer or nanolayer technology involves pre-encapsulating the film prior to entering the cast film or blown film die. This can be produced by a feed block.

[0145] In some preferred embodiments, the coextrusion is a bubble coextrusion process, and the expansion ratio can vary between 0.5 and 2.0, preferably between 0.7 and 1.8, and most preferably between 0.9 and 1.5. Following coextrusion using this expansion ratio, the film can be MD stretched, MD stretched and then TD stretched (with or without MD relaxation), or simultaneous MD and TD stretched. The film can then optionally be calendered to further control porosity.

[0146] Benefits of coextrusion include, but are not limited to, an increased number of layers (interfaces), which is believed to improve puncture strength, without wishing to be bound by any particular theory. Coextrusion is also believed to result in the observed DB improvement, without wishing to be bound by any particular theory. Specifically, the DB improvement may be related to the reduced PP pore size observed when a coextrusion process is used. Coextrusion also allows for a wide range of material options by incorporating blends into the microlayers. Coextrusion also allows for the formation of thin tri- or multi-layer films (coextruded films). For example, tri-layer coextruded films with thicknesses of 8 or 10 microns or less can be formed. Coextrusion allows for higher MD elongation and different pore structures (smaller PP, larger PE). Coextrusion can be combined with lamination to create desired multilayer structures of the present invention, such as those formed in the examples.

[0147] The minimum achievable thickness is determined by the extrusion process. In some examples, the thinnest PP microlayer may be about 0.19 mil (about a 4.83 um sublayer), and the PE about 0.17 mil (about a 4.32 um sublayer). For each of the three microlayers, the PP and PE layers are 0.19 mil and 0.17 mil, respectively. In one example 21-layer structure, the PP may be about 1.14 mil (or 0.57 mil on each side) and the PE may be 0.17 mil, for a total extrusion thickness of 1.31 mil (33 um). We may be able to make a 21-layer product with this configuration that is only 30 mils or less.

[0148] (2) Lamination is not so limited and includes bringing together a surface of the coextruded film with a surface of at least one other film and securing the two surfaces, one to the other, using heat, pressure, and / or heat and pressure. For example, heat may be used to increase the viscosity of either or both surfaces of the coextruded film and at least one other film to facilitate lamination and make the two surfaces sticky or better adhere together.

[0149] 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 before lamination.

[0150] (3) Additional steps The additional steps may include, consist of, or consist essentially of MD, TD, or sequential or simultaneous MD and TD stretching steps. Stretching steps may occur before or after the lamination step. Stretching may be performed with MD and / or TD relaxation. Co-pending, commonly owned U.S. Patent Application Publication No. 2017 / 0084898 A1, published March 23, 2017, is incorporated herein by reference in its entirety.

[0151] Other additional steps may include calendaring. For example, in some embodiments, a calendaring step may be performed as a means of reducing thickness, reducing pore size and / or porosity, and / or to further improve the transverse direction (TD) tensile strength and / or puncture strength of the porous biaxially stretched membrane precursor. Calendaring may also improve strength, wettability, and / or uniformity, and reduce surface layer defects that become incorporated during the manufacturing process, for example, during the MD and TD stretching processes. Calendared films or membranes may have improved coatability (using smooth calendar roll(s)). Additionally, using calendaring rolls may aid in improved coating adhesion to the film or membrane.

[0152] Calendering can be cold (below room temperature), ambient (room temperature), or hot (e.g., 90°C) and can include the application of pressure or the application of heat and pressure to controllably reduce the thickness of the membrane or film. Calendering can be in one or more steps, such as low-pressure calendering followed by higher-pressure calendering, cold calendering followed by hot calendering, etc. The calendering process can also densify the thermosensitive material using at least one of heat, pressure, and speed. The calendering process can also selectively densify the thermosensitive material using uniform or non-uniform heat, pressure, and / or speed, imparting uniform or non-uniform calendering conditions (e.g., by using smooth rolls, rough rolls, patterned rolls, micropatterned rolls, nanopatterned rolls, speed variations, temperature variations, pressure variations, humidity variations, double roll steps, multiple roll steps, or combinations thereof), resulting in improved, desired, or unique structure, characteristics, and / or performance, and / or resulting structure, characteristics, and / or performance, etc.

[0153] Another additional step may include pore filling. The pore filling step is not particularly limited and may be performed in any manner consistent with the goals described herein. For example, in some embodiments, the pores may be partially or completely coated, treated, or filled with a pore filling composition, material, polymer, gel polymer, layer, or vapor deposition (such as PVD). Preferably, the pore filling composition coats 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, etc., of the surface area of ​​the pores. The pore filling composition may comprise, consist of, or consist essentially of a polymer and a solvent. The solvent may be any suitable solvent useful for forming a composition for coating or filling pores, including an organic solvent such as 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 concentration of the polymer in the pore-filling composition can be between 1-30%, between 2-25%, between 3-20%, between 4-15%, between 5-10%, etc., but is not particularly limited as long as the viscosity of the pore-filling composition is such that the composition is capable of coating the walls of the pores of any of the porous biaxially stretched precursor membranes disclosed herein. Pore filling increases either or both the machine direction (MD) and transverse direction (TD) tensile strength. [Example]

[0154] Example Preparations Inventive (multilayer) products were prepared and compared to comparative (three-layer) products. The multilayer products were formed by the method described herein, which includes coextruding three separate films containing three coextruded layers and laminating the three films together. The three-layer products were formed by forming three separate extruded monolayer films and laminating the monolayers together. This was formed.

[0155] The microlayer composition of the product of the present invention prepared was as follows: Example 1 (EX1) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers are homopolymer PP with a MFR ranging from 0.5 MFR to 2 MFR. All PE layers have a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0156] Example 2 (EX2) - (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 high density polyethylene with a melt index of 0.25-0.5 g / 10 min at 2.16 kg and 190°C. PE2 is ultra high density polyethylene. PE3 is melt index of 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 It is a blend of 95% high density polyethylene and 5% mLLDPE. 13 microns thick. Basis weight 0.7 mg / cm 3 . JIS Gurley 245s / 100cc. AQ porosity 41.45%.

[0157] Example 3 (EX3) - (PP / PP / PP) (PE1 / PE2 / PE1) (PP / PP / PP) - PP layer had a density of 0.90 g / cm 3 , made from homopolymer PP with MFR ranging from 0.5 MFR to 2 MFR. PE1 is made from high density polyethylene with a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190 degrees Celsius. PE2 is made from ultra-high molecular weight polyethylene.

[0158] Example 4 (EX4) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers had a density of 0.90 g / cm3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0159] Example 5 (EX5) - PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0160] Example 6 (EX6) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - PP had a density of 0.90 g / cm 3 The PE is made from a homopolymer PP with a MFR ranging from 0.5 MFR to 2 MFR. The PE is made from a high density polyethylene with a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C. The thickness is 16.6 microns. The basis weight is 0.79 mg / cm. 3 . JIS Gurley 198s / 100cc. AQ porosity 45.33%.

[0161] Example 7 - (EX7) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers had a density of 0.90 g / cm 3 , M in the range of 0.5MFR to 2MFR It is made from FR homopolymer PP. All PE layers have a melt index of 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 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0162] Example 8 (EX8) - (PP1 / PP2 / PP1) (PE1 / PE2 / PE1) (PP1 / PP2 / PP1) PP1 had a density of 0.90 g / cm 3 , made from homopolymer PP with MFR ranging from 0.5 MFR to 2 MFR. PP2 is made from homopolymer PP with MFR of 0.25 and density of 0.9. PE1 is a high density polyethylene with a melt index of 0.25-0.5 g / 10 min at 2.16 kg and 190 degrees Celsius. PE2 is an ultra-high molecular weight polyethylene.

[0163] Example 9 (EX9) - (PP1 / PP2 / PP1) (PE / PE / PE) (PP1 / PP2 / PP1) - PP1 had a density of 0.90 g / cm 3 PP2 is made from homopolymer PP with MFR ranging from 0.5 MFR to 2 MFR. PP2 has a density of 0.90 g / cm3. 3 , a blend of 95% homopolymer PP with a range of 0.5MFR to 2MFR and 5% propylene-ethylene copolymer. PE is a blend of 92% high-density polyethylene with a melt index of 0.25 to 0.5g / 10min at 2.16kg and 190°C and 8% olefin block copolymer.

[0164] Example 10 (EX10) - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0165] 27-39 and additional multilayer embodiments, with primary reference now to additional Examples 11-38: Example 11 - Each PP and PE layer of the three-layer structure is itself composed of multiple layers, preferably coextruded and then laminated - (PP / PP / PP) (PE / PE / PE) (PP / PP / PP) - all PP layers have a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0166] Example 12 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same as or a different blend or block copolymer from PP1, PP2.

[0167] Example 13 - (PP1 / PP1) or (PP2 / PP2) or (PP1 / PP2) - PP1 is a polypropylene blend and PP2 is a PP block copolymer.

[0168] Example 14 - (PP1 / PP1 / PP1) or (PP2 / PP2 / PP2) - PP1 is a polypropylene blend and PP2 is a PP block copolymer.

[0169] Example 15 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is a mixture of the same or different PP blocks. It is a copolymer.

[0170] 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 a different PP block copolymer.

[0171] 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 a different PP block copolymer.

[0172] Example 18 - (PP1 / PP2) / (PP3 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or a different PP block copolymer.

[0173] Example 19 - (PP1 / PP2 / PP3 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 is the same or a different PP block copolymer.

[0174] Example 20 - (PP1 / PP2 / PP3) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PP3 contains an adhesion promoter.

[0175] Example 21 - (PO3 / PP2 / PP1) - PP1 is a polypropylene blend, PP2 is a PP block copolymer, and PO3 is a polyolefin blend (e.g., PP+PE).

[0176] Example 22 - (PP1 / PP2 / PP3) - PP1 is (homopolymer PP) + (any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane). PP2 is the same or different homopolymer PP as used in PP1, including copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is (homopolymer PP, same or different from those used in PP1 and PP2) + (surface coefficient of friction (COF) modifying additive, same or different from that used in PP1).

[0177] Example 23 - (PP3 / PP2 / PP1) - PP1 is a homopolymer PP plus any slip or block additive, e.g., a coefficient of friction (COF) modifying additive as described herein, which may include siloxane. PP2 is the same or different homopolymer PP as used in PP1 and PP3 plus a copolymer PP, which may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is the same or different homopolymer PP as used in PP1 and PP2 plus a surface coefficient of friction modifying additive, which may be the same or different as used in PP1.

[0178] Example 24 - (PP3 / PP2 / PP1) or (PP1 / PP2 / PP3) - PP1 is (homopolymer PP) + (any slip or block additive, e.g., a coefficient of friction (COF) modifying additive as described herein, which may include siloxanes). PP2 is (the same or different homopolymer PP as used in PP1 and PP3) + (copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer). PP3 is (the same or different homopolymer PP as used in PP1 and PP2) (homopolymer PP) + (copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer or elastomer).

[0179] Example 25: A coextruded PP precursor is proposed with the following structure: Homopolymer PP + additives to modify the surface COF --------------------------------- Homopolymer PP + Copolymer PP --------------------------------- Homopolymer PP + additives to modify the surface COF The surface modifying additives may include any slip or anti-blocking additive, such as siloxane. The copolymer may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer or elastomer.

[0180] The coextruded PP precursor can be extruded at a BUR (Bullet Roll Under) of 0.9 to 1.5 to control the porosity. The coextruded PP precursor can then be subsequently MD-then TD-stretched or simultaneously biaxially stretched. The biaxially stretched film can be further calendered to control the porosity.

[0181] Example 26: A second proposed structure could be as follows for battery separator or textile applications:

[0182] PP Blend 1------------------------ PP block copolymer 2------------------------ PP block copolymer

[0183] This structure can be designed for a higher tortuosity surface layer for water barrier in high viscosity water tests.

[0184] The types of copolymers that can be incorporated into the structure include, but are not limited to, propylene-ethylene or ethylene-propylene random copolymers, block copolymers or elastomers.

[0185] By extruding PP in a coextrusion format, the surface characteristics of the PP layer can be modified, and at the same time, a lower melting point copolymer resin can be incorporated into the interlayer to lower the shutdown temperature. Different copolymer resins can also be incorporated anywhere in the structure to control the porosity of the TD-oriented film.

[0186] The incorporation of BUR in the precursor film also allows for further control of the porosity required for different applications.

[0187] 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 a different PP block copolymer.

[0188] Example 28 - (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) - PP1 is a polypropylene blend and PP2 is a PP block. copolymer, and PP3 is the same or a different PP block copolymer.

[0189] Example 29 - (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 a different PP block copolymer.

[0190] 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 a different PP block copolymer.

[0191] 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 a different PP block copolymer.

[0192] 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 a different PP block copolymer.

[0193] Example 33 - (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3) - PP1 is a homopolymer PP plus any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane. PP2 is the same or different homopolymer PP as used in PP1 and PP3 plus a copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is the same or different homopolymer PP as used in PP1 and PP2 plus a surface coefficient of friction modifying additive, the same or different from that used in PP1.

[0194] Example 34—(PP3 / PP2 / PP1) / (PP3 / PP2 / PP1) / (PP3 / PP2 / PP1)—PP1 is a homopolymer PP plus any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane. PP2 is the same or different homopolymer PP as used in PP1 and PP3 plus a copolymer PP, which may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is the same or different homopolymer PP as used in PP1 and PP2 plus a surface coefficient of friction modifying additive, the same or different from that used in PP1.

[0195] Example 35 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) PP1 is a homopolymer PP plus any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane. PP2 is the same or different homopolymer PP as used in PP1 and PP3 plus a copolymer PP, which may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is the same or different homopolymer PP as used in PP1 and PP2 plus a surface coefficient of friction modifying additive, the same or different from that used in PP1.

[0196] Example 36 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) PP1 is (homopolymer PP) + (any slip or block additive) PP1 is a homopolymer PP (same or different from that used in PP1 and PP2) plus a copolymer PP, which may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP2 is a homopolymer PP (same or different from that used in PP1 and PP2) plus a surface coefficient of friction modifying additive (same or different from that used in PP1).

[0197] Example 37 - (PP1 / PP2 / PP3) (PP3 / PP2 / PP1) (PP3 / PP2 / PP1) PP1 is a homopolymer PP plus any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane. PP2 is the same or different homopolymer PP as used in PP1 and PP3 plus a copolymer PP, which may be any propylene-ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer. PP3 is the same or different homopolymer PP as used in PP1 and PP2 plus a surface coefficient of friction modifying additive, the same or different from that used in PP1.

[0198] Example 38 - (PP3 / PP2 / PP1) (PP1 / PP2 / PP3) (PP1 / PP2 / PP3): PP1 is (homopolymer PP) + (any slip or block additive, e.g., a coefficient of friction modifying additive as described herein, which may include siloxane). PP2 is (the same or different homopolymer PP as used in PP1 and PP3) + (copolymer PP, which may be any propylene ethylene or ethylene-propylene random copolymer, block copolymer, or elastomer). PP3 is (the same or different homopolymer PP as used in PP1 and PP2) + (surface coefficient of friction modifying additive, the same or different from that used in PP1).

[0199] Example 39 - (RO417): Same as Example 2 except with 7% mL LDPE. Thickness is 12.5 microns. Basis weight is 0.62 mg / cm 2 The JIS Gurley is 200s / 100cc. The AQ porosity is 44.4%.

[0200] Example 40 - (R0416) (PP / PP / PP) / (PE / PE / PE) / (PP / PP / PP). All PP layers have a density of 0.90 g / cm. 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from high density polyethylene with a thickness of 14.9 microns and a basis weight of 0.75 mg / cm. 2 The JIS Gurley is 172s / 100cc. The AQ porosity is 44.2%.

[0201] Example 41 - Structure 1 shown in Figure 53 was made by forming a first sub-membrane by co-extruding 0.1 mil PE, 0.1 mil PP, and a 0.1 mil PE blend. A second sub-membrane was formed by co-extruding 0.47 mil PP, 0.47 mil PP, and 0.47 mil PP. One second sub-membrane was then laminated between two first sub-membranes to form the multi-layer microporous membrane of Figure 64.

[0202] This construction achieves low pin removal force and better interlayer adhesion. The PE outer layer provides reduced pin removal force. The PE blend (lower melting) at the interface provides improved interaction adhesion. The thin PE layer improves puncture strength. In some embodiments, In this case, the PP layer may be a PP blend that improves adhesion and other properties.

[0203] Example 42 - Structure 2, shown in Figure 54, was fabricated by co-extruding 0.07 mil PE, 0.53 mil PP, and 0.07 mil PE to form a first sub-membrane. Three first sub-membranes were then laminated together to form the microporous membrane of Structure 2.

[0204] The purpose of this construction is to provide many benefits compared to PE / PP / PE products. The purpose of this construction is to provide low pin removal force (outer layer) and a comparable interfacial layer. The PE outer layer of the first sub-membrane can provide reduced pin removal force while simultaneously solving the intra-layer adhesion problem. The thin PE also improves puncture strength. In some embodiments, the PP resin can be a high molecular weight PP resin.

[0205] Example 43 - Structure 3 shown in Figure 55 was made by forming a first sub-membrane by co-extruding 0.095 mil PE, five 0.095 mil PP, and one 0.095 mil PP. Three of the first sub-membranes were then laminated together.

[0206] This structure is similar to Structure 2 in Figure 54, for example, except that the PP portion of the first sub-membrane includes five distinct microlayers instead of one. This structure has all the benefits of Structure 2, including the additional benefits resulting from the increased number of microlayers in the first sub-membrane.

[0207] Example 44 Structure 4, shown in Figure 56, was fabricated by forming a first sub-membrane by co-extruding a 0.133 mil blend of polypropylene and polysiloxane, 0.133 mil polypropylene, and 0.133 mil polypropylene. The second sub-membrane was formed by co-extruding 0.2 mil polypropylene, 0.2 mil polyethylene blend, and 0.2 mil blend of polypropylene and propylene-ethylene elastomer. In a first lamination step, the first and second sub-membranes were laminated together as shown in Figure 56, and then the laminates formed in the first lamination step were laminated together such that the microlayers made from polypropylene and propylene-ethylene elastomer contacted in the final product.

[0208] This example exhibits high DB, passes nail penetration, and exhibits good compression. The amount of polysiloxane is 3%.

[0209] Example 45 Structure 5, shown in Figure 57, was fabricated by forming a first sub-membrane by co-extruding a 0.133 mil blend of polypropylene and polysiloxane, 0.133 mil polypropylene, and 0.133 mil polypropylene. The second sub-membrane was formed by co-extruding a 0.2 mil polyethylene blend, 0.2 mil polypropylene, and a 0.2 mil blend of polypropylene and propylene-ethylene elastomer. In a first lamination step, the first sub-membrane was laminated to the second sub-membrane as shown in Figure 57, and then the laminates formed in the first lamination step were laminated together such that the microlayers made from polypropylene and propylene-ethylene elastomer contacted in the final product.

[0210] This example has a high DB, passes nail penetration, and has good compression. 3% polysiloxane is added.

[0211] Example 46 Structure 6 shown in Figure 58 was prepared by mixing 0.11 mm of PP and polysiloxane, The first sub-membrane was fabricated by co-extruding 0.11 mm polypropylene, 0.11 mm polyethylene blend, 0.11 mm polyethylene blend, 0.11 mm polypropylene, and a 0.11 mm blend of polypropylene and polysiloxane. The second sub-membrane was fabricated by co-extruding 0.11 mm PP, 0.11 mm PP and propylene-ethylene copolymer, 0.11 mm polyethylene, 0.11 mm polyethylene, 0.11 mm PP and propylene-ethylene copolymer, and 0.11 mm polypropylene. The two first sub-membranes were then laminated on either side of a single second sub-membrane to form the final product, as shown in Figure 58.

[0212] This product has 18 layers with 17 interfacial layers, has a high DB, passes nail penetration, and has good compression. It contains 3% polysiloxane.

[0213] Example 47 Structure 7, shown in Figure 59, was fabricated by forming a first sub-membrane by co-extruding a 0.19 mm blend of PP and 6% ultra-high molecular weight polysiloxane (slip agent or antiblocking agent), 0.19 mm PP, and 0.19 mm PP containing 10% propylene-ethylene elastomer. The second sub-membrane was formed by co-extruding three 0.21 mm blends of polyethylene and 5% metallocene linear low-density polyethylene (mLLDPE). The third sub-membrane was formed by co-extruding a 0.19 mm blend of PP and 10% propylene-ethylene copolymer, 0.19 mm PP, and a 0.19 mm blend of PP and 10% propylene-ethylene copolymer. All PP layers had a density of 0.90 g / cm. 3The PEs were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PEs had melt indices of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and densities ranging from 0.955 to 0.966 g / cm. 3 It is a high density polyethylene.

[0214] In the first lamination step, two second sub-membranes were laminated on either side of a single third sub-membrane, as shown in Figure 59. In the second lamination step, two first sub-membranes were laminated on either side of the laminate formed in the first step, with the microlayers containing PP.

[0215] Example 48 Structure 8, shown in Figure 60, was fabricated by co-extruding 0.11 mm PP, 0.11 mm PP / propylene-ethylene elastomer blend, 0.11 mm PE blend, 0.11 mm PE blend, 0.11 mm PP / propylene-ethylene elastomer blend, and 0.11 mm PP to form a first sub-membrane. The second sub-membrane was also co-extruded with 0.11 mm PP / propylene-ethylene elastomer, 0.11 mm PP, 0.11 mm PE, 0.11 mm PE, 0.11 mm PP, and 0.11 mm PP / propylene-ethylene elastomer. In the lamination step, two first sub-membranes were laminated on either side of a single second sub-membrane. This lamination (lam.) is shown in Figure 60.

[0216] Example 49 A multi-layer microporous membrane was formed containing 5% maleic anhydride modified HDPE and polypropylene in at least one outermost nano- or micro-layer. Some properties of this example are reported in Figure 61.

[0217] Example 50 Multilayer microporous membranes were formed containing 10% maleic anhydride-modified homo-PP in at least one outermost nano- or micro-layer. Some properties of the two multilayer microporous membranes of this example are reported in Figures 61 and 62. SEM images of Example 52 are in Figures 63 and 64.

[0218] Example 51 A multi-layer microporous membrane was formed containing 10% maleic anhydride modified coPP in at least one outermost nano- or micro-layer. Some properties of this example are reported in Figures 61 and 62. An SEM image of Example 51 is in Figure 63.

[0219] Example 52 A multilayer microporous membrane was formed with at least one outermost nano- or micro-layer containing 15% maleic anhydride-modified homo-PP. Some properties of this example are reported in Figure 62. SEM images of Example 52 are in Figures 63 and 64.

[0220] Example 53 5% styrene-ethylene-propylene-styrene (SEPS) copolymer and density = 0.90 g / cm 3 Multilayer microporous membranes were formed containing homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR in at least one outermost nano- or micro-layer. Some properties of this example are reported in Figure 76.

[0221] In another example, a styrene-ethylene-butylene-styrene copolymer may be used in place of the SEPS copolymer.

[0222] Example 54 10% maleic anhydride modified homo-PP, 5% styrene-ethylene-propylene-styrene (SEPS) copolymer, and density = 0.90 g / cm 3 Multilayer microporous membranes were formed containing homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR in at least one outermost nano- or micro-layer. Some properties of this example are reported in Figure 76.

[0223] In another example, a styrene-ethylene-butylene-styrene copolymer may be used in place of the SEPS copolymer.

[0224] Example 55 5% propylene-ethylene elastomer, 10% maleic anhydride modified homo-PP, and density = 0.90 g / cm 3 Multilayer microporous membranes were formed containing homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR in at least one outermost nano- or micro-layer. Some properties of this example are reported in Figure 76.

[0225] Example 56 Multilayer microporous membrane formed using a collapsed bubble method. The membrane has a thickness of 10 microns and is formed by coextruding PP1 / PP1 / PE1 and collapsing the bubbles to form a product having the structure PP1 / PP1 / PE1 / PE1 / PP1 / PP1. PP1 is a homopolymer polypropylene with a melt index of 1.0-3.0 g / 10 min. PE1 is a high-density polyethylene with a melt index of 0.1-0.5 g / 10 min. A 5000x SEM of this embodiment is shown in Figure 67, and data for Example 56 can be found in the table in Figure 68.

[0226] Example 57 A multilayer microporous membrane formed using a collapsed cell method. The membrane has a thickness of approximately 10 microns and is formed by coextrusion of PP1 / PP1 / PP2 and collapsing the cells to form a product having the structure PP1 / PP1 / PP2 / PP2 / PP1 / PP1. PP1 is a homopolymer polypropylene having a melt index of 1.0-2.5 g / 10 min. PP2 is a blend of PP1 and a homopolymer PP with an MFR of 4.5-6. A 5000x SEM of this embodiment is shown in FIG. 66, and data for Example 57 can be found in the table in FIG.

[0227] Example 58 Adhesive coated multi-layer microporous membranes are prepared and subjected to a nail penetration test, the results of which are shown in Figure 71, which shows the layer following the nail.

[0228] Example 59 Multilayer microporous membranes with the structure (PP1 / PP1 / PP1 / ) / (PE1 / PE1 / PE1) / (PP1 / PP1 / PP1) and a thickness of 16 microns were fabricated. PP1 is polypropylene with an MFR of 0.7-1.0. PE1 is a blend of polyethylene homopolymer with an MI of 0.2-0.4 and 5% mLLDPE.

[0229] The layer composition of certain comparative products was prepared as follows: Comparative Example 1 (COM EX1) - (PP) / (PE) / (PP) - all PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0230] Comparative Example 2 (COM EX2) - (PP) / (PE) / (PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0231] Comparative Example 3 (COM EX3) - (PP) / (PE) / (PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0232] Comparative Example 4 (COM EX4) - (PP) / (PE) / (PP) - All PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0233] Comparative Example 5 (COM EX5) - (PP) / (PE) / (PP) - all PP layers had a density of 0.90 g / cm 3 The PE layers were made from homopolymer PP with MFRs ranging from 0.5 MFR to 2 MFR. All PE layers had a melt index of 0.25 to 0.5 g / 10 min at 2.16 kg and 190°C and a density range of 0.955 to 0.966 g / cm. 3 It is made from a blend of 95% high density polyethylene and 5% mLLDPE.

[0234] Comparative Example 6 (H2013) - (PP) / (PE) / (PP) - Thickness 20.5 microns, empty Porosity 45%, Gurley 325 seconds. All PP layers have a density of 0.90 g / cm 3 The PE layer has a melt index of 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 It is a high density polyethylene.

[0235] Comparative Example 7 (2320) - (PP) / (PE) / (PP)PE layer has a melt index of 2.16 kg and 190°C of 0.25 to 0.5 g / 10 min and a density range of 0.955 to 0.966 g / cm3 The PP is a homopolymer PP similar to PP1 in Example 2. The thickness is 20 microns, the porosity is 40%, and the Gurley is 536 seconds.

[0236] Comparative Example 8 (C210)-(PP) / (PE) / (PP): All PP layers had a density of 0.90 g / cm 3 The PE layer has a melt index of 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 High density polyethylene. 16 microns thick. Porosity is 38%. Gurley is 450 seconds.

[0237] Comparative Example 9 (R0367) - (PP) / (PE)(PP): All PP layers had a density of 0.90 g / cm 3 The PE layer has a melt index of 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 It is a blend of 95% high density polyethylene and 5% mLLDPE. It is 12 microns thick. The porosity is 39%. The Gurley is 264 seconds.

[0238] Comparative Example 10: Multi-layer microporous membrane with no additives, specifically no maleic anhydride modified polymer. Data for Comparative Example 10 can be found in Figures 61, 62, and 76. SEMs of Comparative Example 10 are in Figures 63 and 64.

[0239] Comparative Example 11: A coextruded tri-layer product formed by coextruding three layers together to form the structure PP1 / PE1 / PP1, where PE1 is a high density polyethylene having a melt index of 0.2-0.6 g / 10 min, and PP1 is a polypropylene having an MFR in the range of 0.7-1.0. The total thickness is 10 microns. Data for Comparative Example 11 can be found in the table in Figure 70.

[0240] Characterization of Examples—Separator-Related Properties and Battery Performance Thickness (μm) Thickness is measured in micrometers (μm) using an Emveco Microgage 210-A micrometer thickness tester and test procedure ASTM D374. The thicknesses of Examples 1 and 6 and Comparative Examples 3 and 4 were determined and are reported in the table in FIG. 61. Comparative examples with thicknesses corresponding to the Examples were prepared so that the separators could be meaningfully compared. All thicknesses disclosed herein were measured using this method.

[0241] Basic weight (mg / cm 2 ) The basis weights of Examples 1 and 6 and Comparative Examples 3 and 4 were determined and are reported in the table in Figure 61. All basis weights disclosed herein were measured using this method.

[0242] JIS Gurley (s / 100cc) Gurley is defined herein as Japanese Industrial Standard (JIS Gurley) and is measured herein using an OHKEN Permeability Tester. JIS Gurley is defined as the time (seconds) required for 100 cc of air to pass through 1 square inch of film at a constant pressure of 4.9 inches of water. The JIS Gurleys of Examples 1 and 6 and Comparative Examples 3 and 4 were measured. These are reported in the table in Figure 61. All Gurley values ​​disclosed herein were measured using this method. The Gurley of coated products is typically higher than the corresponding uncoated products.

[0243] MD shrinkage at 120℃ (%) Shrinkage is measured by placing a test sample between two paper sheets, then clipping them together to hold the sample between the sheets and suspending it in an oven. For the 1 hour 120°C test, the sample is placed in a 120°C oven for 1 hour. After the indicated heating time in the oven, each sample is removed and attached to a flat opposing surface using double-sided adhesive tape, and the sample is flattened and smoothed to obtain accurate length and width measurements. Shrinkage is measured in both the machine direction (MD) and the transverse direction (TD) and is expressed as MD shrinkage (%) and TD shrinkage (%). The MD shrinkage of Example 1 and SR0367 was measured and is reported in the table in Figure 63. As shown in this figure, the multilayer example showed significantly lower MD shrinkage at 120°C. All MD (%) shrinkage values ​​at 120°C were measured using this method.

[0244] MD shrinkage at 150℃ (%) Shrinkage was measured by placing a test sample between two sheets of paper, then clipping them together to hold the sample between the sheets and suspending it in an oven. For the 1 hour 150°C test, the sample was placed in a 150°C oven for 1 hour. After the indicated heating time in the oven, each sample was removed and attached to an opposite flat surface using double-sided adhesive tape, and the sample was flattened and smoothed to obtain accurate length and width measurements. Shrinkage was measured in both the machine direction (MD) and the transverse direction (TD) and is expressed as MD shrinkage (%) and TD shrinkage (%). All MD (%) shrinkage values ​​at 150°C were measured using this method.

[0245] Elasticity Elasticity was assessed using dynamic mechanical analysis under the following conditions: Equipment: RSA-G2 (TA instrument) Temperature -140℃~170℃ Rate 5°C / min Distortion: 0.2% Frequency: 1Hz The results are shown in the figure. Tangent (Delta) = Loss Modulus (E') / Storage Modulus (E").

[0246] Storage modulus (E"), loss modulus (E') and tangent (delta) were measured over the temperature range of -140°C to 170°C for Examples 1 and 2 and Example R0417. These values ​​were also measured for 2320 (comparative example). The results can be found in Figures 34-43.

[0247] TD elongation at break (%) TD elongation at break (%) is the percentage of elongation of the test sample along the cross direction of the test sample measured at the maximum tensile strength required to break the sample. The TD elongations of Examples 1 and 6 and Comparative Examples 3 and 4 were measured and are reported here. Data for Examples 1 and 6 and Comparative Examples 3 and 4 are included in Figure 51.

[0248] Compressibility: Compression or compressibility was measured using the compression recovery or "springback" method. The test procedure is as follows: Probe: Use a probe with a hemispherical shape. Round it for minimum contact with the surface. Preload force: 0.020 N A 1 cm x 1 cm sample is compressed at 0.25 N / min up to 0.50 N, then the pressure is released at 0.25 N / min down to 0.01 N. This is done at ambient temperature.

[0249] The percent dimensional change upon compression and recovery is estimated based on the initial thickness of the sample.

[0250] Data for Examples 1 and 6 and Comparative Examples 3 and 4 are shown in Figures 49 and 50.

[0251] Characterization of Examples—Structural Properties AQ porosity (%) The porosity of the microporous film samples was measured using ASTM method D-2873 and is defined as the percentage voids in the microporous membrane measured in both the machine direction (MD) and the cross direction (TD). The AQ porosities for Examples 1 and 6 and Comparative Examples 3 and 4 were calculated and are reported in the table in Figure 61. Some additional porosity data for Example 1 was determined and is reported in Table 1 below:

[0252] [Table 1]

[0253] Aquapore porosity (%) Aquapore (AQ) porosity was measured for Examples 1 and 6 and Comparative Examples 3 and 4. These are reported in the table in FIG.

[0254] Calculated bending degree. The degree of bending was calculated using the following formula (1): N m =T 2 / P(1) In the formula, N m is the MacMullin number, T is the tortuosity, and P is the porosity. While not wishing to be bound by any particular theory, it is believed that the more tortuosity a battery separator has, the safer it is. This is because, due to the more tortuous path that growing dendrites must follow from the anode to the cathode, it is believed to be more difficult for dendrites to grow between the electrodes. The calculated tortuosity for Examples 1 and 6 and Comparative Examples 3 and 4 is given in the table in FIG. 61.

[0255] SEM images 1. Pre-processing conditions Procedure for cross-sectional observation using a scanning electron microscope (SEM). a.) Cut the sample to an appropriate size (a few mm square). b.) Ion milling produces a flat cross section (MD-ND plane). Ion milling equipment: E-3500 (Hitachi High-Technologies Corporation.) Ion source: Ar+ Accelerating voltage: 3.5 kV Discharge voltage: 2.0 kV Stage control: 5 (setting value) Processing time: 4 hours Temperature: 20~25℃ c.) Mount the sample on the stub using double-sided carbon conductive tape and carbon paste. d.) Apply an osmium plasma coating to make the sample conductive.

[0256] 2. SEM observation conditions a. Equipment: S-4800 (Hitachi High-Technologies Corporation.) Acceleration voltage: 1 kV Working distance: approx. 5 mm SEM images were taken of Examples 1, 2, 4, and 6 and Comparative Examples 1, 4, and 5. Some of these images are shown in Figures 17-23. It was found that there were distinct structural differences between the multilayer products in the Examples and the three-layer products in the Comparative Examples. For example, the PP layers of the three-layer products contained more columnar or vertically continuous amorphous regions, while the amorphous regions of the multilayer (having three PP layers in the Examples) PP regions were largely discontinuous and non-columnar. Side-by-side comparisons in Figures 21-23 illustrate these differences between the multilayer and three-layer products.

[0257] Machine Learning Exam Detailed Steps 1: Image feature extraction to obtain vectors for machine learning ·Read image using OpenCV python module cv2 Obtain 50 240x160 pixel^2 subimages at uniformly random locations throughout the PP or PE region and normalize the images using cv2.normalize with α=0, β=255 and norm_type=cv2.NORM_MINMAX. For each subimage, we use the SIFT feature detector cv2.xfeatures2d.SIFT_create with default settings to obtain features with angle and size. Convert each angle a of the obtained feature to a'=90-|a mod 180-90| For i from 1 to 9, called the bin count, [10 * (i-1), 10 * Count the number of angles a' transformed in the range [i] Concatenate the bin count, average feature size (a scalar), and number of features (a scalar) to obtain the feature vector x k (11 dimensions) (kth image) · Take the median values ​​of 11 features from the 50 partial images and use them as the feature vector x of the input image.

[0258] Rules for the OpenCV python module cv2 include Python Machine Learning by Sebastian Raschka (ISBN 1783555130) and OpenCV by Python Blueprints by Michael Beyeler (1785282697), both of which are incorporated herein by reference in their entirety. More information about OpenCV can be found at https: / / en.wikipedia.org / wiki / OpenCV

[0259] Example of PP layer: Obtain the feature vector x from the PP layer by following step 1 below. Each value x in x is calculated using the mean vector m=[0.130044,0.097145,0.064741,0.046804,0.041001,0.04556,0.067887,0.146754,0.356967,3.491879,592.693] and standard deviation vector s=[0.015042,0.011565,0.01036,0.009822,0.009092,0.009514,0.012442,0.015578,0.065252,0.16019,61.84486]. xm) / s. Let w be [-1.93271,-0.11236,0.881572,0.610045,0.108711,-0.19117,-0.23341,-0.25129,0.316427,-0.85435], and the dot product w T Calculate x' do ·w T If x'>0.474451, classify the image as 9 layers.

[0260] Example of PE layer: Obtain the feature vector x from the PE layer by following step 1 below. Standardize each value x in x as x' = (xm) / s using the following mean vector m = [0.060457, 0.055388, 0.047194, 0.04173, 0.041355, 0.047016, 0.068816, 0.145675, 0.485289, 3.485506, 463.3455] and standard deviation vector s = [[0.016258, 0.012571, 0.006678, 0.005956, 0.006548, 0.007862, 0.011579, 0.01748, 0.050551, 0.149306, 60.23634]. w = [0.425456,-0.54632,- 0.3682, 0.325934, 0.218774, -0.0182, 1.330079, 0.318507, -1.16948, -2.13611, -0.72327], and the inner product w T Calculate x'. ·w T If x'>-0.0609, classify the image as 9 layers.

[0261] Examples 1, 2, 4, 6, and 39, and Comparative Examples 1, 3, 4, 5, 6, 7, 8, and 9 were subjected to machine learning testing to determine whether the comparative (three-layer) examples and the inventive (multi-layer) examples could be distinguished by the testing. The results are in Figures 25 and 26. The comparative (three-layer) examples and the inventive (multi-layer) examples could be distinguished using the machine learning testing.

[0262] high speed puncture In this method, a 1.25" x 40" sample of microporous material is equilibrated for 20 minutes in a temperature and humidity controlled environment. The sample is then inserted into a tungsten carbide circular tip knee. The needle is punctured with a needle. The tip has a 0.5 mm radius and the test is run at 25 mm / min. The process is repeated every inch until 30 data points are collected. The average of these data points is reported as the puncture. For the puncture average, two puncture measurements are averaged. Some puncture data, including high-speed puncture data obtained using puncture speeds greater than 25 mm / min, is shown in Figure 69.

[0263] According to at least selected embodiments, the present application, disclosure, or invention relates to new or improved membranes, separator films, 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, 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 making and / or using such membranes, separator films, 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 articles of manufacture comprising same. According to at least certain embodiments, the present disclosure or invention relates to new or improved membrane layers, membranes, or separator films, battery separators comprising such membranes, and / or related methods. According to at least certain 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 certain embodiments, the present disclosure or invention relates to new or improved microporous polyolefin membranes or separator membranes, microlayer membranes, multilayer membranes including one or more microlayers or nanolayer membranes, battery separators including such membranes, and / or related methods. According to at least certain specific embodiments, the present disclosure or invention relates to new, optimized, or improved microporous stretched polymer membranes or separator membranes having one or more new or improved outer and / or inner layers, microlayer membranes, multilayer microporous membranes or separator membranes having outer and inner layers, some of which layers or sublayers are produced by coextrusion and then laminated together to form the new, optimized, or improved membrane or separator membrane. In some embodiments, a given layer, microlayer, or nanolayer may comprise a homopolymer, copolymer, block copolymer, elastomer, and / or polymer blend.In selected embodiments, at least certain layers, microlayers, or nanolayers may comprise different or distinct polymers, homopolymers, copolymers, block copolymers, elastomers, and / or polymer blends. The present disclosure or invention also relates to new or improved methods of making such membranes, separator membranes, or separators, and / or methods of using such membranes, separator membranes, 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 microlayer porous or microporous membranes, separator membranes, separators, composites, electrochemical devices, and / or batteries, and / or methods of making and / or using such membranes, separators, composites, devices, and / or batteries. According to at least certain selected embodiments, the present application or invention is directed to new or improved separator membranes that are multilayered, where one or more layers of the multilayer structure are produced in a multilayer or microlayer coextrusion die by multiple extruders. The new or improved membrane, separator membrane, or separator may preferably demonstrate new or improved structure, performance, utilization, such as improved shutdown, improved strength, improved dielectric breakdown strength, improved elongation, improved puncture strength, improved high speed puncture strength, lower Gurley, reduced crystallization, and / or reduced tendency to tear, and combinations thereof.

[0264] According to at least selected embodiments, the present application or invention provides a method for improving battery performance. The present application or invention is directed to additives for secondary lithium batteries, membranes containing improved additives, improved battery separators, and / or improved batteries, and / or improved or related methods of making and / or using the same. According to at least certain embodiments, the present application or invention is directed to additive-containing membranes, separator membranes, and / or battery separators, and / or methods of making and / or using such membranes, separator membranes, and / or battery separators. According to at least particular embodiments, the present application or invention is directed to the incorporation of additives into microporous or separator membranes used in secondary lithium batteries, e.g., secondary lithium-ion batteries, improved battery separators, and / or related methods. In some embodiments, the membranes can include additives that improve performance in battery chemistries, e.g., lithium-ion batteries. In other selected embodiments, the membranes can include additives, e.g., siloxanes or lithium stearate, that improve pin removal performance. In certain other embodiments, the present invention may also relate to methods of making such membranes or separator membranes and methods of using such membranes or separator membranes, for example, as lithium battery separators. According to at least selected embodiments, the present application or invention is directed to new or improved porous membranes, separator membranes, 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 embodiments, new or improved membrane or separator structures, performance, and / or uses, such as improved shutdown, improved strength, improved dielectric breakdown strength, improved elongation, improved puncture strength, improved high-speed puncture strength, lower Gurley, reduced crystallization, and / or reduced tear tendency, and combinations thereof, are provided, addressed, or disclosed. According to at least certain selected embodiments, the present invention is directed to new or improved separator membranes that include additives or elastomers. The improved membrane may preferably demonstrate improved shutdown, improved strength, improved dielectric breakdown strength, and / or reduced tendency to tear.According to at least 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 comprises an additive. The additive may be selected from the group consisting of lubricants, plasticizers, nucleating agents, shrinkage reducers, surfactants, SEI improvers, cathode protectants, flame retardant additives, LiPF salt stabilizers, overcharge protectants, aluminum corrosion inhibitors, lithium deposition agents or improvers, or solvation promoters, aluminum corrosion inhibitors, wetting agents, thickeners, friction reducers, COF reducers, pin removal force reducers, copolymers, block copolymers, and / or combinations thereof. Also described herein are batteries, including primary or secondary lithium-ion batteries, that include one or more of the described films, membranes, coatings, and / or separators. Methods for making the films, membranes, coatings, and / or battery separators are also described.According to at least certain embodiments, the present application or invention provides an improved or novel battery separator having at least one of increased puncture strength, reduced pin removal force, improved electrolyte wettability, and increased pore size; a battery separator comprising at least one of a microporous polymer film having an optional coating layer on at least one side of the microporous polymer film; a microporous polymer film having an optional coating and an additive therein and / or thereon selected from the group consisting of a lubricant, a surfactant, a nucleating agent, a shrinkage reducing agent, and / or a plasticizer; a microporous polymer film having an additive present primarily in or throughout at least one surface region thereof, present in a single surface region thereof, present in a first surface region thereof and a second surface region opposite the first surface region; a coating applied to a surface of the microporous polymer film, which coating may be applied to only one surface of the microporous polymer film or may be applied to the first side of the microporous polymer film and a separate coating applied to a second side opposite the first side of the microporous polymer film. The present invention is directed to the above-mentioned coatings, and / or combinations thereof, which may be added to the film, coating, or separator. According to at least some preferred embodiments, the microporous polymer film or membrane is a microporous polyolefin membrane, such as a dry-stretched process membrane, such as a single-layer dry-process film, a two-layer dry-process film, or a multilayer dry-process film. Also, according to at least some preferred embodiments, one, two, three, four, or all five of the different types of additives may be added, or a single additive may be added to the film, coating, or separator that acts as one, two, three, four, or all five of the different types of additives, such as an additive that is both a lubricant and a surfactant.

[0265] The microporous multilayer battery separators described herein, in some embodiments, exhibit improved safety, strength, and durability compared to prior bilayer, trilayer, or multilayer battery separators. For example, such separators may exhibit increased average dielectric breakdown (DB), increased minimum DB, increased shutdown speed, and increased flexure, all indicative of a safer battery separator. The separators may also exhibit increased puncture strength and increased mixed penetration values, indicative of a stronger, more durable battery.

[0266] These properties of the microporous multilayer battery separators described herein are at least partially a result of the method by which they are made. In some embodiments, this method includes at least coextruding two or more polymer mixtures to form a first coextruded bi-, tri-, or multilayer film, coextruding two or more other polymer mixtures to form a second coextruded bi-, tri-, or multilayer film, and coextruding two or more additional polymer mixtures to form a third coextruded bi-, tri-, or multilayer film. Coextrusion typically involves using a coextrusion die with one or more extruders (typically one extruder per layer of the bi-, tri-, or multilayer film) feeding the die. The polymer mixtures used to form each layer of the first, second, and third bi-, tri-, or multilayer films can be the same or different. The mixtures can include only one polymer or more than one polymer, e.g., polymer blends. Also, more than three bi-, tri-, or multilayer films can be formed. After the first, second, and third bilayer, trilayer, or multilayer films are formed, the films are laminated together with two of the films formed on opposing surfaces of one of the films to form the microporous battery separator described herein.

[0267] 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.

[0268] The battery separators herein may be described in several different ways.

[0269] In a first aspect, a battery separator for a lithium battery is described herein. In some embodiments, the battery separator includes at least one microporous separator membrane or sub-membrane including a plurality of porous or microporous polymer microlayers or nanolayers, wherein at least one of the individual microlayers or nanolayers includes a different or different polymer, molecular weight polymer, homopolymer, copolymer, and / or polymer blend, includes a different or different additive, agent, material, and / or filler, or includes a different or different polymer, molecular weight polymer, homopolymer, copolymer, and / or polymer blend, compared to an adjacent individual microlayer or nanolayer. The separator membranes or sub-membranes may comprise a combination of polymers, homopolymers, copolymers, polymer blends, additives, agents, materials, and / or fillers. In some embodiments, multiple separator membranes or sub-membranes of polymer microlayers or nanolayers are laminated to each other or to a microporous polymer membrane. In some embodiments, at least one of the separator membranes or sub-membranes of polymer microlayers or nanolayers has at least three microlayers or nanolayers. Sometimes, at least one of the separator membranes or sub-membranes of polymer microlayers or nanolayers is made from one or more polyolefins. Sometimes, at least one of the separator membranes or sub-membranes of polymer microlayers or nanolayers is comprised of a coextruded, dry-process polyolefin microlayer or nanolayer. In some embodiments, at least two of the separator membranes or sub-membranes of polymer microlayers or nanolayers. In some embodiments, at least three of the separator membranes or sub-membranes of polymer microlayers or nanolayers.

[0270] Described herein are multilayer microporous films or membranes that can exhibit improved properties, including improved dielectric breakdown and strength, compared to previous monolayer or trilayer microporous membranes of the same thickness. Preferred multilayer microporous membranes include microlayers and one or more lamination interfaces or barriers. Also disclosed are battery separators or batteries that include one or more of the multilayer microporous films or membranes. The batteries and battery separators of the present invention are preferably safer and more robust than batteries and battery separators that use previous monolayer and trilayer microporous membranes. Also described herein are methods for making the multilayer microporous separators, membranes, or films described herein.

[0271] Various embodiments of the present invention have been described in order to achieve various objects of the present invention. It is to be understood that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

[0272] The present invention may be embodied in other forms without departing from its spirit and essential characteristics, and therefore, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the present invention. Components that can be used to implement the disclosed methods and systems are disclosed. These and other components are disclosed herein, and combinations, subsets, interactions, groups, etc. of these components are understood to be specifically contemplated and described herein with respect to all methods and systems, even though their respective various individual collective combinations and arrangements may not be expressly disclosed. This applies to all aspects of the present application, including, but not limited to, steps in the disclosed methods. Thus, when there are various additional steps that can be implemented, it is understood that these additional steps can each be implemented by any specific embodiment or combination of embodiments of the disclosed methods.

[0273] The above written descriptions of structures and methods are presented for illustrative purposes only. Examples are used to disclose exemplary embodiments, including the best mode, and to enable one skilled in the art to practice the invention, including making and using any devices or systems and practicing any incorporated methods. These examples are not intended to be exhaustive or to limit the invention to the precise steps and / or configurations disclosed, and many modifications and variations are possible in light of the above teachings. For example, the invention or embodiments may be particularly well suited for dry-process foam extrusion and laminated films or precursors, but may also be used for other processes, such as dry-process slot die, dry-process slot die coextrusion, wet-process slot die, wet-process slot die coextrusion, BNBOPP cast film, BNBOPP cast film coextrusion, etc. Other films or precursors, such as extrusion, cascaded slot die extrusion, laminated versions, coated products, etc., are similarly covered and described. The features described herein may be combined in any combination. The steps of the methods described herein may be performed in any order that is physically possible. The patentable scope of the invention is defined by the appended claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims when they have structural elements that do not differ from the literal language of the claims, or when they have equivalent structural elements that have insubstantial differences from the literal language of the claims.

[0274] 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 in addition to those shown and described herein are intended to be within the scope of the appended claims. Moreover, although only certain representative compositions and method steps disclosed herein have been specifically recited, other combinations of such compositions and method steps are also intended to be within the scope of the appended claims even if not specifically recited. Thus, although combinations of steps, elements, components, or elements may be explicitly recited below, other combinations of steps, elements, components, or elements are included even if not explicitly recited.

[0275] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates 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 the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the statement includes cases where such event or circumstance occurs and cases where it does not occur.

[0276] Throughout this detailed description and claims, the word "comprise" and variations of that word, such as "comprising" and "comprises," 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, which are also disclosed. "Exemplary" or "for example" means "an example of" and is not intended to convey an indication of a preferred or ideal embodiment. Similarly, "such as" is used in a limiting sense, but for descriptive or illustrative purposes.

[0277] Except as otherwise stated, all numbers expressing geometric shapes, dimensions, and the like used in the specification and claims should be understood as at least as numbers and should be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the application of the doctrine of equivalents to the claims.

[0278] Unless otherwise defined, all technical and scientific terms used herein Terms 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 to which they cite are specifically incorporated by reference.

[0279] Moreover, the invention illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

Claims

1. 1. A multi-layer microporous membrane or film comprising: (a) having at least one additive in at least one layer of said multi-layer microporous membrane or film; (b) having or exhibiting increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multi-layer microporous membrane or film; (c) having or exhibiting an increased or improved elongation at break (TD) compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multi-layer microporous membrane or film; (d) said multi-layer microporous membrane or film has or exhibits reduced high temperature shrinkage at 150°C compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup; (e) said multi-layer microporous membrane or film has or exhibits reduced high temperature shrinkage at 120°C compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup; (f) having at least one layer comprising a polymer blend; (g) having a nonwoven or woven fabric attached to one or both sides of the multilayer microporous membrane or film; (h) and combinations thereof; The multi-layer microporous membrane or film has or exhibits at least one of:

2. 10. The multilayer microporous membrane or film of claim 1 having at least one additive in at least one layer thereof.

3. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive is present in one or both outermost layers of the multi-layer microporous membrane or film.

4. 4. The multi-layer microporous membrane or film of claim 3, wherein the at least one additive is present in one of the outermost layers of the multi-layer microporous membrane or film.

5. 4. The multi-layer microporous membrane or film of claim 3, wherein the at least one additive is present in both of the outermost layers of the multi-layer microporous membrane or film.

6. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive is present in at least one inner layer of the multi-layer microporous membrane or film.

7. 6. The multi-layer microporous membrane or film of claim 4 or 5, wherein the at least one additive is also present in at least one inner layer of the multi-layer microporous film or membrane.

8. 3. The multi-layer microporous membrane or film of claim 2, wherein each layer has a different composition than each adjacent layer.

9. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a functional polymer.

10. 10. The multi-layer microporous membrane or film of claim 9, wherein the functional polymer is a maleic anhydride modified polymer.

11. 11. The multi-layer microporous membrane or film of claim 10, wherein the maleic anhydride modified polymer is maleic anhydride modified homopolymer polypropylene, copolymer polypropylene, high density polypropylene, or low density polypropylene.

12. 11. The multilayer microporous membrane or film of claim 10, wherein the maleic anhydride modified polymer is a maleic anhydride modified homopolymer polyethylene, copolymer polyethylene, high density polyethylene, or low density polyethylene.

13. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises an ionomer.

14. 14. The multilayer microporous membrane or film of claim 13, wherein the ionomer is a Li-based ionomer, a Na-based ionomer, or a Zn-based ionomer.

15. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises cellulose nanofibers.

16. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises inorganic particles having a narrow particle size distribution.

17. The inorganic particles are SiO ２ particles, TiO ２ 17. The multi-layer microporous membrane or film of claim 16, wherein the at least one of the at least one of the following is selected from the group consisting of: a polymer, a polymerizable polymer, a polymerizable compound, a polymerizable polymeric ...

18. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a lubricant.

19. 20. The multi-layer microporous membrane or film of claim 18, wherein the lubricant is amphiphilic.

20. 20. The multi-layer microporous membrane or film of claim 19, wherein the lubricant is a fatty acid salt.

21. 21. The multi-layer microporous membrane or film of claim 20, wherein the fatty acid salt is selected from at least one of lithium stearate and sodium stearate.

22. 20. The multi-layer microporous membrane or film of claim 18, wherein the lubricant is a compound containing one or more siloxy functional groups, including a siloxane or polysiloxane.

23. 23. The multi-layer microporous membrane or film of claim 22, wherein the lubricant is an ultra-high molecular weight polysiloxane.

24. The multi-layer microporous membrane or film of claim 2 , wherein the at least one additive comprises a nucleating agent.

25. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a cavitation enhancing agent.

26. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a fluoropolymer.

27. 27. The multi-layer microporous membrane or film of claim 26, wherein the fluoropolymer is PVDF.

28. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a cross-linking agent.

29. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises an x-ray detectable material.

30. 30. The multi-layer microporous membrane or film of claim 29, wherein the x-ray detectable material is barium sulfate.

31. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a lithium halide.

32. 32. The multi-layer microporous membrane or film of claim 31 , wherein the lithium halide is lithium iodide.

33. 3. The multi-layer microporous membrane or film of claim 2, wherein the at least one additive comprises a polymer processing agent.

34. 3. The multilayer microporous membrane or film of claim 2, wherein the at least one additive comprises a high temperature melt index (HTMI) polymer.

35. 35. The multi-layer microporous membrane or film of claim 34, wherein the HTMI polymer is at least one selected from PMP, PMMA, PET, PVDF, aramid, syndiotactic polystyrene, and combinations thereof.

36. The multi-layer microporous membrane or film of claim 2 , wherein the additive comprises an electrolyte additive.

37. The electrolyte additives include an SEI improver, a cathode protectant, a flame retardant additive, LiPF ６ 3. The multilayer microporous membrane or film of claim 2, wherein the additive is at least one selected from the group consisting of a salt stabilizer, an overcharge protectant, an aluminum corrosion inhibitor, a lithium deposition agent or improver, or a solvation promoter, an aluminum corrosion inhibitor, a wetting agent, and a thickener.

38. 8. The multilayer microporous membrane or film of any one of claims 1 to 7, wherein the membrane or film is coated on one or both sides thereof, and the coating on one or both sides of the film comprises at least one additive.

39. 10. The multilayer microporous membrane or film of claim 1, having or exhibiting increased or improved elasticity at 150°C or above compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

40. 40. The multilayer microporous membrane or film of claim 39, wherein the tangent (delta) of the membrane or film is greater than -0.6 at 150°C as measured by dynamic mechanical analysis.

41. 40. The multilayer microporous membrane or film of claim 39, wherein the tangent (delta) of the membrane or film is between -1.0 and -0.6 at temperatures between 175°C and 200°C as measured by dynamic mechanical analysis.

42. 42. The multilayer microporous membrane or film of claim 41, wherein the tangent (delta) is between -0.9 and -0.6 at temperatures between 175°C and 200°C.

43. 43. The multilayer microporous membrane or film of claim 42, wherein the tangent (delta) is between -0.8 and -0.6 at temperatures between 175°C and 200°C.

44. 44. The multilayer microporous membrane or film of claim 43, wherein the tangent(delta) is between -0.7 and -0.6 at temperatures between 175°C and 200°C.

45. 40. The multilayer microporous membrane or film of claim 39, wherein the tangent (delta) of the membrane or film is greater than -1.2 at temperatures of 200°C or greater as measured by dynamic mechanical analysis.

46. 46. ​​The membrane or film of claim 45, wherein tan(delta) is greater than -1.0 at temperatures of 200°C or greater.

47. 47. The multilayer microporous membrane or film of claim 46, wherein tan(delta) is greater than -0.8 at temperatures of 200°C or greater.

48. 10. The multilayer microporous membrane or film of claim 1, having or exhibiting increased or improved compressibility compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

49. 49. The multi-layer microporous membrane or film of claim 48, having a percent recovery greater than 9% as measured by the compression recovery method.

50. 50. The multi-layer microporous membrane or film of claim 49, wherein the percent recovery is greater than 9.5% as measured by the compression recovery method.

51. 51. The multi-layer microporous membrane or film of claim 50, having a % Recovery greater than 10.0% as measured by the Compression Recovery Method.

52. 52. The multi-layer microporous membrane or film of claim 51, having a % Recovery greater than 10.1% as measured by the Compression Recovery Method.

53. 53. The multi-layer microporous membrane or film of claim 52, having a % Recovery greater than 10.2% as measured by the Compression Recovery Method.

54. 54. The multi-layer microporous membrane or film of claim 53, having a % Recovery greater than 10.3% as measured by the Compression Recovery Method.

55. 55. The multi-layer microporous membrane or film of claim 54, having a % Recovery greater than 10.4% as measured by the Compression Recovery Method.

56. 56. The multi-layer microporous membrane or film of claim 55, having a % recovery greater than 10.5% as measured by the Compression Recovery Method.

57. 10. The multilayer microporous membrane or film of claim 1, having or exhibiting increased or improved elongation at break (TD) compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

58. 58. The multilayer microporous membrane or film of claim 57, wherein the elongation at break (TD) is more than 30% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film.

59. 59. The multilayer microporous membrane or film of claim 58, wherein the elongation at break (TD) is more than 35% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film.

60. 60. The multilayer microporous membrane or film of claim 59, wherein the elongation at break (TD) is more than 40% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film.

61. 61. The multilayer microporous membrane or film of claim 60, wherein the elongation at break (TD) is more than 41% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin configuration as the multilayer microporous membrane or film.

62. 62. The multilayer microporous membrane or film of claim 61, wherein the elongation at break (TD) is more than 42% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film.

63. 63. The multilayer microporous membrane or film of claim 62, wherein the elongation at break (TD) is more than 45% higher compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as the multilayer microporous membrane or film.

64. 10. The multilayer microporous membrane or film of claim 1, having or exhibiting reduced high temperature shrinkage at 120°C compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

65. 65. The multilayer microporous membrane or film of claim 64, wherein the high temperature shrinkage at 120°C is 30-75% lower compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

66. 66. The multilayer microporous membrane or film of claim 65, wherein the high temperature shrinkage at 120°C is 35-70% lower compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

67. 67. The multilayer microporous membrane or film of claim 66, wherein the high temperature shrinkage at 120°C is 35-65% lower compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

68. 68. The multilayer microporous membrane or film of claim 67, wherein the high temperature shrinkage at 120°C is 40-60% lower compared to a three-layer microporous membrane having the same thickness, Gurley, porosity, and / or resin makeup as said multilayer microporous membrane or film.

69. 10. The multilayer microporous membrane or film of claim 1, wherein at least one layer of the membrane or film comprises a polymer blend.

70. 70. The multi-layer microporous membrane or film of claim 69, wherein the at least one layer is an outer layer.

71. 70. The multi-layer microporous membrane or film of claim 69, wherein the at least one layer is an inner layer.

72. 70. The multilayer microporous membrane or film of claim 69, wherein the polymer blend comprises at least two different polyolefins.

73. 70. The multilayer microporous membrane or film of claim 69, wherein the polymer blend comprises at least two different polyethylenes.

74. 70. The multilayer microporous membrane or film of claim 69, wherein the polymer blend comprises at least two different polypropylenes.

75. 70. The multi-layer microporous membrane or film of claim 69, wherein the polymer blend comprises polyethylene and polypropylene.

76. 70. The multilayer microporous membrane or film of claim 69, wherein the polymer blend comprises a polyolefin and a non-polyolefin.

77. 70. The multi-layer microporous membrane or film of claim 69, wherein each layer of the membrane or film has a different composition than adjacent layers.

78. 10. The multi-layer microporous membrane or film of claim 1 having a nonwoven or woven fabric attached to one or both sides of the multi-layer microporous membrane or film.

79. 79. The multilayer microporous membrane or film of claim 78, wherein a nonwoven or woven fabric is attached to one side of the multilayer microporous film or membrane.

80. 79. The multilayer microporous membrane or film of claim 78, wherein a nonwoven or woven fabric is attached to both sides of the multilayer microporous film or membrane.

81. 10. The multi-layer microporous membrane or film of claim 1, having a total thickness of less than 30 microns.

82. 82. The multi-layer microporous membrane or film of claim 81, having a total thickness of less than 25 microns.

83. 83. The multi-layer microporous membrane or film of claim 82, having a total thickness of less than 20 microns.

84. 84. The multi-layer microporous membrane or film of claim 83, having a total thickness of less than 15 microns.

85. 85. The multi-layer microporous membrane or film of claim 84, having a total thickness of less than 10 microns.

86. 86. The multilayer microporous membrane or film of any one of claims 81-85, wherein the multilayer microporous film comprises at least three layers that are all microlayers (1-10 microns thick), all nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers.

87. 86. The multilayer microporous membrane or film of any one of claims 81-85, wherein the multilayer microporous film comprises at least four layers that are all microlayers (1-10 microns thick), all nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers.

88. 86. The multilayer microporous membrane or film of any one of claims 81-85, wherein the multilayer microporous film comprises at least five layers that are all microlayers (1-10 microns thick), all nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers.

89. 86. The multilayer microporous membrane or film of any one of claims 81-85, wherein the multilayer microporous film comprises at least six layers that are all microlayers (1-10 microns thick), all nanolayers (less than 1 micron thick), or a combination of nanolayers and microlayers.

90. 1. A multilayer microporous film comprising a region, the film comprising two or more layers and polyethylene in one or more of said layers, wherein the region, when tested by the machine learning test described herein, satisfies the following: W Ｔ x ' ≧−2.0 or W Ｔ x ' ≧−1.0 The multi-layer microporous membrane or film.

91. The following is satisfied: W Ｔ x ' ≧0.0 or W Ｔ x ' ≧2.0 91. The multi-layer microporous membrane or film of claim 90.

92. A multilayer microporous membrane or film comprising a region, the multilayer microporous membrane or film comprising two or more layers and polypropylene in one or more of the layers, wherein the region, when tested by the machine learning test described herein, satisfies the following: W Ｔ x ' ≧−1.5 or W Ｔ x ' ≧−1.0 The multi-layer microporous membrane or film.

93. The following is satisfied: W Ｔ x ' ≧0.5 or W Ｔ x ' ≧1.5 93. The multi-layer microporous membrane or film of claim 92.

94. Two outermost sub-membranes comprising three or more nanolayers (less than 1 micron thick) or microlayers (between 1 and 10 microns thick); and At least one inner sub-membrane comprising three or more nanolayers (less than 1 micron thick) or microlayers (between 1 and 10 microns thick) comprising, consisting of, or consisting essentially of polypropylene A multi-layer microporous membrane or film comprising: The multi-layer microporous membrane or film, wherein in at least one of the outermost sub-membranes, the outermost microlayer or nanolayer comprises, consists of, or consists essentially of polyethylene.

95. 95. The multilayer microporous membrane or film of claim 94, wherein in said at least one outermost sub-membrane, said innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend.

96. 95. The multilayer microporous membrane or film of claim 94, wherein the at least one outermost sub-membrane has an outermost microlayer or nanolayer comprising, consisting of, or consisting essentially of polyethylene and an innermost microlayer or nanolayer comprising, consisting of, or consisting essentially of a polyethylene blend.

97. 95. The multilayer microporous membrane or film of claim 94, wherein in both of said outermost sub-membranes, the outermost microlayer or nanolayer comprises, consists of, or consists essentially of polyethylene.

98. 98. The multilayer microporous membrane or film of claim 97, wherein in both of the outermost sub-membranes, the innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend.

99. 99. The multilayer microporous membrane or film of any one of claims 95, 96, or 98, wherein the at least one inner sub-membrane is in direct contact with at least one of the outermost sub-membranes whose innermost microlayer or nanolayer comprises, consists of, or consists essentially of a polyethylene blend.

100. 95. The multilayer microporous membrane or film of claim 94, wherein the membrane or film comprises another inner sub-membrane comprising at least three nano- or micro-layers, and at least one outermost micro- or nano-layer of the another inner sub-membrane comprises, consists of, or consists essentially of a polyethylene blend.

101. 101. The multilayer microporous membrane or film of claim 100, wherein the outermost microlayers or nanolayers of both of said separate inner sub-membranes comprise, consist of, or consist essentially of a polyethylene blend.

102. 95. The multilayer microporous membrane or film of claim 94, wherein the nanolayers or microlayers of the outermost sub-membrane are thinner than the nanolayers or microlayers of the innermost sub-membrane.

103. 103. The multilayer microporous membrane or film of claim 102, wherein the nano- or micro-layers of the outermost sub-membrane are 2 to 5 times thinner than the nano- or micro-layers of the innermost sub-membrane.

104. 104. The multilayer microporous membrane or film of claim 103, wherein the nano- or micro-layers of the outermost sub-membrane are 3 to 5 times thinner than the nano- or micro-layers of the innermost sub-membrane.

105. 105. The multilayer microporous membrane or film of claim 104, wherein the nano- or micro-layers of the outermost sub-membrane are 4 to 5 times thinner than the nano- or micro-layers of the innermost sub-membrane.

106. 95. The multi-layer microporous membrane or film of claim 94, wherein the membrane or film comprises 10-35% polyethylene, based on the total weight of the membrane or film.

107. 107. The multi-layer microporous membrane or film of claim 106, wherein the membrane or film comprises 15-25% polyethylene, based on the total weight of the membrane or film.

108. 1. A multi-layer microporous membrane or film comprising: In two outermost sub-membranes comprising at least three nanolayers (less than 1 micron thick) or microlayers (1-10 microns thick) (or two outermost nanolayers or microlayers and at least one inner nanolayer or microlayer), the two outermost nanolayers or microlayers of the outermost sub-membranes are an outermost sub-membrane having a nano- or microlayer thinner than at least one inner nano- or microlayer of the outermost sub-membrane; and At least one inner sub-membrane comprising at least three nano- or micro-layers (or two outermost nano- or micro-layers and at least one inner nano- or micro-layer), wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are thinner than at least one inner nano- or micro-layer of the at least one inner sub-membrane. The multi-layer microporous membrane or film comprising:

109. 109. The multilayer microporous membrane or film of claim 108, wherein the two outermost nanolayers or microlayers of the outermost sub-membrane are 10-95% thinner than the at least one inner nanolayer or microlayer of the outermost sub-membrane.

110. 110. The multilayer microporous membrane or film of claim 109, wherein the two outermost nanolayers or microlayers of the outermost sub-membrane are 50-90% thinner than the at least one inner nanolayer or microlayer of the outermost sub-membrane.

111. 111. The multilayer microporous membrane or film of claim 110, wherein the two outermost nanolayers or microlayers of the outermost sub-membrane are 60-90% thinner than the at least one inner nanolayer or microlayer of the outermost sub-membrane.

112. 112. The multilayer microporous membrane or film of claim 111, wherein the two outermost nanolayers or microlayers of the outermost sub-membrane are 70-90% thinner than the at least one inner nanolayer or microlayer of the outermost sub-membrane.

113. 113. The multilayer microporous membrane or film of claim 112, wherein the two outermost nanolayers or microlayers of the outermost sub-membrane are 80-90% thinner than the at least one inner nanolayer or microlayer of the outermost sub-membrane.

114. 109. The multilayer microporous membrane or film of claim 108, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are 10-95% thinner than the at least one inner nano- or micro-layer of the at least one inner sub-membrane.

115. 115. The multilayer microporous membrane or film of claim 114, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are 50-90% thinner than the at least one inner nano- or micro-layer of the at least one inner sub-membrane.

116. 116. The multilayer microporous membrane or film of claim 115, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are 60-90% thinner than the at least one inner nano- or micro-layer of the at least one inner sub-membrane.

117. 117. The multilayer microporous membrane or film of claim 116, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are 70-90% thinner than the at least one inner nano- or micro-layer of the at least one inner sub-membrane.

118. 118. The multilayer microporous membrane or film of claim 117, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane are 80-90% thinner than the at least one inner nano- or micro-layer of the at least one inner sub-membrane.

119. The two outermost nano- or micro-layers of the at least one inner sub-membrane are 110. The multilayer microporous membrane or film of claim 109, wherein the at least one inner nano- or microlayer is 10-95% thinner than the at least one inner nano- or microlayer of at least one inner sub-membrane.

120. 109. The multilayer microporous membrane or film of claim 108, wherein the outermost nano- or microlayer of the outermost sub-membrane comprises, consists of, or consists essentially of polyethylene.

121. 109. The multilayer microporous membrane or film of claim 108, wherein the outermost nano- or microlayer of the at least one inner sub-membrane comprises, consists of, or consists essentially of polyethylene.

122. 121. The multilayer microporous membrane or film of claim 120, wherein the outermost nano- or microlayer of the at least one inner sub-membrane comprises, consists of, or consists essentially of polyethylene.

123. 109. The multilayer microporous membrane or film of claim 108, wherein the at least one inner nano- or micro-layer of the outermost sub-membrane comprises, consists of, or consists essentially of polypropylene.

124. 121. The multilayer microporous membrane or film of claim 120, wherein the at least one inner nano- or micro-layer of the outermost sub-membrane comprises, consists of, or consists essentially of polypropylene.

125. 123. The multilayer microporous membrane or film of claim 122, wherein the at least one inner nano- or microlayer of the outermost sub-membrane comprises, consists of, or consists essentially of polypropylene.

126. 126. The multilayer microporous membrane or film of any one of claims 123-125, wherein the polypropylene is a high molecular weight polypropylene.

127. 109. The multi-layer microporous membrane or film of claim 108, comprising 10 to 35 wt% polyethylene, based on the total weight of the multi-layer microporous membrane.

128. 110. The multi-layer microporous membrane or film of claim 109, comprising 10 to 35 weight percent polyethylene, based on the total weight of the multi-layer microporous membrane.

129. 115. The multi-layer microporous membrane or film of claim 114, comprising 10 to 35 weight percent polyethylene, based on the total weight of the multi-layer microporous membrane.

130. 120. The multi-layer microporous membrane or film of claim 119, comprising 10 to 35 weight percent polyethylene, based on the total weight of the multi-layer microporous membrane.

131. 124. The multi-layer microporous membrane or film of claim 123, comprising 10 to 35 wt% polyethylene, based on the total weight of the multi-layer microporous membrane.

132. 109. The multilayer microporous membrane or film of claim 108, wherein the outer sub-membrane and the at least one inner sub-membrane are each separately formed by coextrusion.

133. each of the sub-membranes formed by coextrusion is laminated to at least one other sub-membrane formed by coextrusion to form the multi-layer microporous membrane or film; 133. The multilayer microporous membrane or film of claim 132.

134. 109. The multi-layer microporous membrane of claim 108, wherein the membrane or film has a thickness of 1 to 30 microns.

135. 1. A multi-layer microporous membrane or film comprising: two outermost sub-membranes comprising two outermost nano- or micro-layers (less than 1 micron thick) and at least one inner nano- or micro-layer, wherein the outermost nano- or micro-layers of the two outermost sub-membranes comprise, consist of, or consist essentially of polyethylene, and the at least one inner nano- or micro-layer of the two outermost sub-membranes comprises, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene; and At least one inner sub-membrane comprising two outermost nano- or micro-layers and at least one inner nano- or micro-layer, wherein the two outermost nano- or micro-layers of the at least one inner sub-membrane comprise, consist of, or consist essentially of polyethylene, and the at least one inner nano- or micro-layer of the at least one inner sub-membrane comprises, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene. The multi-layer microporous membrane or film comprising:

136. 136. The multilayer microporous membrane or film of claim 135, wherein the outermost sub-membrane comprises two or more inner nano- or micro-layers, and the at least one inner sub-membrane comprises two or more inner nano- or micro-layers.

137. 137. The multilayer microporous membrane or film of claim 136, wherein the outermost sub-membrane comprises three or more inner nano- or micro-layers, and the at least one inner sub-membrane comprises three or more inner nano- or micro-layers.

138. 138. The multilayer microporous membrane or film of claim 137, wherein the outermost sub-membrane comprises four or more inner nano- or micro-layers, and the at least one inner sub-membrane comprises four or more inner nano- or micro-layers.

139. 139. The multilayer microporous membrane or film of claim 138, wherein the outermost sub-membrane comprises five or more inner nano- or micro-layers, and the at least one inner sub-membrane comprises five or more inner nano- or micro-layers.

140. 140. The multilayer microporous membrane or film of any one of claims 136-139, wherein all of the inner nano- or micro-layers comprise, consist of, or consist essentially of polypropylene, including high molecular weight polypropylene.

141. 136. The multilayer microporous membrane or film of claim 135, wherein the membrane or film comprises 10 to 35 weight percent polyethylene, based on the total weight of the membrane or film.

142. 136. The multilayer microporous membrane or film of claim 135, wherein the membrane or film comprises 15 to 25 weight percent polyethylene, based on the total weight of the membrane or film.

143. 136. The multilayer microporous membrane or film of claim 135, wherein the sub-membranes are formed by coextrusion.

144. 144. The multilayer microporous membrane or film of claim 143, wherein each of the coextruded submembranes is laminated to at least one other of the coextruded submembranes to form the multilayer microporous membrane or film.

145. 1. A multi-layer microporous membrane or film comprising: two outermost sub-membranes comprising two or more nanolayers (less than 1 micron thick) or microlayers (1-10 microns thick), wherein the outermost nanolayer or microlayer of the outermost sub-membranes, which are also the outermost nanolayer or microlayer of the multilayer microporous membrane or film, comprises a siloxane or polysiloxane; and At least one inner sub-membrane comprising two or more nano- or micro-layers The multi-layer microporous membrane or film comprising:

146. 146. The multilayer microporous membrane or film of claim 145, wherein the polysiloxane is present in an amount of 1 to 10 wt % or 1 to 30% based on the total weight of the nano- or microlayers of the outermost sub-membrane comprising the siloxane or polysiloxane.

147. 146. The multilayer microporous membrane or film of claim 145, wherein there are two inner sub-membranes, and the inner and outermost sub-membranes each have three or more microlayers or nanolayers.

148. 148. The multilayer microporous membrane or film of claim 147, wherein the outermost nanolayers or microlayers of each of the inner sub-membranes are in contact with each other in the multilayer microporous membrane or film and comprise, consist of, or consist essentially of the same resin.

149. 148. The multilayer microporous membrane or film of claim 147, wherein the outermost nanolayers or microlayers of each of the inner sub-membranes are in contact with each other in the multilayer microporous membrane or film and have the same composition.

150. 148. The multilayer microporous membrane or film of claim 147, wherein the outermost nanolayer or microlayer of each inner sub-membrane is in contact with the outermost nanolayer or microlayer of the outermost sub-membrane, and the outermost nanolayer or microlayer of each inner sub-membrane comprises, consists of, or consists essentially of the same resin as the outermost nanolayer or microlayer of the outermost sub-membrane with which it is in contact.

151. 151. The multilayer microporous membrane or film of claim 150, wherein the outermost nanolayer or microlayer of each inner sub-membrane has the same composition as the outermost nanolayer or microlayer of the contacting outermost sub-membrane.

152. 146. The multilayer microporous membrane or film of claim 145, wherein there is one inner sub-membrane, and the inner sub-membrane and the outermost sub-membrane each have six or more microlayers or nanolayers.

153. 153. The multilayer microporous membrane or film of claim 152, wherein both outermost microlayers or nanolayers of the outermost sub-membranes comprise polysiloxane or siloxane.

154. 154. The multilayer microporous membrane or film of claim 153, wherein the polysiloxane is present in an amount of 1 to 10 wt %, based on the total weight of the microlayer or nanolayer.

155. 155. The multilayer microporous membrane or film of any one of claims 153-154, wherein the outermost microlayer or nanolayer of the outermost sub-membrane also comprises polypropylene.

156. 156. The multilayer microporous membrane or film of any one of claims 153-155, wherein the outermost microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of polypropylene.

157. 157. The multilayer microporous membrane or film of any one of claims 152-156, wherein the inner microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of at least one of polypropylene, a polypropylene blend, polyethylene, or a polyethylene blend.

158. 158. The multilayer microporous membrane or film of claim 157, wherein the inner microlayer or nanolayer of the inner sub-membrane comprises, in that order, a PP microlayer or nanolayer, a PE blend microlayer or nanolayer, a PE blend microlayer or nanolayer, and a PP microlayer or nanolayer.

159. 159. The multilayer microporous membrane or film of any one of claims 152-158, wherein the inner microlayer or nanolayer of the outermost sub-membrane comprises, consists of, or consists essentially of at least one of polypropylene, polypropylene blends, polyethylene, or polyethylene blends.

160. 160. The multilayer microporous membrane or film of claim 159, wherein the inner microlayer or nanolayer of the outermost sub-membrane comprises, in that order, a PP microlayer or nanolayer, a PE blend microlayer or nanolayer, a PE blend microlayer or nanolayer, and a PP microlayer or nanolayer.

161. 146. The multilayer microporous membrane or film of claim 145, wherein there are three or more inner sub-membranes, and each of the inner and outermost sub-membranes comprises three or more microlayers or nanolayers.

162. 162. The multilayer microporous membrane or film of claim 161, wherein there are three inner sub-membranes, and each of the inner and outermost sub-membranes comprises three microlayers or nanolayers.

163. 163. The multilayer microporous membrane or film of claim 162, wherein the microlayers or nanolayers of two of the inner sub-membranes each comprise, consist of, or consist essentially of polyethylene.

164. 164. The multilayer microporous membrane or film of claim 163, wherein the microlayers or nanolayers of two of the inner sub-membranes each consist of or consist essentially of polyethylene.

165. 165. The multilayer microporous membrane or film of claim 163 or claim 164, wherein the nano- or micro-layers of one of the inner sub-membranes each comprise, consist of, or consist essentially of polypropylene.

166. 166. The multilayer microporous membrane or film of claim 165, wherein the one inner sub-membrane having a nanolayer or microlayer comprising, consisting of, or consisting essentially of polypropylene comprises, in that order, a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend, a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend, and a nanolayer or microlayer comprising, consisting of, or consisting essentially of a polypropylene blend.

167. Nanolayers or microlayers comprising, consisting of, or consisting essentially of polyethylene The multilayer microporous membrane or film of claim 165 or 166, wherein the two inner sub-membranes having nanolayers and the one inner sub-membrane having a nanolayer or microlayer comprising, consisting of, or essentially consisting of polypropylene are arranged in the following order: sub-membrane having a nanolayer or microlayer comprising, consisting of, or essentially consisting of polyethylene; sub-membrane having a nanolayer or microlayer comprising, consisting of, or essentially consisting of polypropylene; and sub-membrane having a nanolayer or microlayer comprising, consisting of, or essentially consisting of polyethylene.

168. 168. The multilayer microporous membrane or film of any one of claims 161-167, wherein the nano- or micro-layers of the outermost sub-membrane each individually comprise, consist of, or consist essentially of polypropylene alone, a blend of polypropylene with another resin, or a blend of polypropylene and polysiloxane.

169. 169. The multilayer microporous membrane or film of claim 168, wherein the outermost sub-membrane comprises, consists of, or consists essentially of, in that order, a nanolayer or microlayer made of a blend of polypropylene and polysiloxane, a nanolayer or microlayer made of polypropylene, and a nanolayer or microlayer made of a blend of polypropylene and another resin.

170. 170. The multilayer microporous membrane or film of any one of claims 161 to 169, wherein the membrane or film comprises 10 to 30 wt% polyethylene, based on the total weight of the membrane or film.

171. 146. The multilayer microporous membrane or film of claim 145, wherein the microlayers or nanolayers all have the same thickness.

172. 146. The multilayer microporous membrane or film of claim 145, wherein the microlayers or nanolayers do not all have the same thickness.

173. 146. The multilayer microporous membrane or film of claim 145, wherein each of said sub-membranes is formed by coextrusion.

174. 174. The multilayer microporous membrane or film of claim 173, wherein each of the coextruded submembranes is laminated to at least one other coextruded submembrane to form the multilayer microporous membrane.

175. 146. The multilayer microporous membrane or film of claim 145, comprising 10 to 35 wt% polyethylene, based on the total weight of the membrane or film.

176. 176. The multilayer microporous membrane or film of claim 175, comprising 15 to 25 wt% polyethylene, based on the total weight of the membrane or film.

177. 1. A multi-layer microporous membrane or film comprising: Two outermost sub-membranes comprising six or more nanolayers (having a thickness of less than 1 micron) or microlayers (having a thickness between 1 and 10 microns); and At least one inner sub-membrane comprising six or more nano- or micro-layers The multi-layer microporous membrane or film comprising:

178. 178. The multilayer microporous membrane or film of claim 177, wherein there is one inner sub-membrane, and said inner sub-membrane and said two outermost sub-membranes comprise six microlayers or nanolayers.

179. The outermost microlayer or nanolayer of the outermost sub-membrane comprises or consists of polypropylene.

179. The multilayer microporous membrane or film of claim 178, consisting essentially of, or

180. 180. The multilayer microporous membrane or film of claim 179, wherein the outermost microlayer or nanolayer of the outermost sub-membrane consists of or consists essentially of polypropylene.

181. 181. The multilayer microporous membrane or film of any one of claims 178-180, wherein the outermost microlayer or nanolayer of the inner sub-membrane comprises, consists of, or consists essentially of a blend of polypropylene and another resin.

182. 182. The multi-layer microporous membrane of claim 181, wherein the outermost microlayer or nanolayer of the inner sub-membrane consists of, or consists essentially of, a blend of polypropylene and another resin.

183. 183. The multilayer microporous membrane or film of any one of claims 178-182, wherein the two microlayers or nanolayers intermediate the two outermost sub-membranes and the inner sub-membrane comprise, consist of, or consist essentially of polyethylene.

184. 184. The multilayer microporous membrane or film of claim 183, wherein the two outermost sub-membranes and the two middle micro- or nano-layers of the inner sub-membrane consist of or consist essentially of polyethylene.

185. 185. The multilayer microporous membrane or film of claim 183 or 184, wherein the two middle microlayers or nanolayers of the two outermost sub-membranes are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the two outermost sub-membranes is one microlayer or nanolayer comprising, consisting of, or consisting essentially of a blend comprising polypropylene and another resin.

186. 186. The multilayer microporous membrane or film of claim 185, wherein the two middle microlayers or nanolayers of the two outermost sub-membranes are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the two outermost sub-membranes is one microlayer or nanolayer consisting of or consisting essentially of a blend comprising polypropylene and another resin.

187. 187. The multilayer microporous membrane or film of any one of claims 183-186, wherein the two middle microlayers or nanolayers of the inner sub-membrane are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the inner sub-membrane is one nanolayer or microlayer comprising, consisting of, or consisting essentially of polypropylene.

188. 188. The multilayer microporous membrane or film of claim 187, wherein the two middle microlayers or nanolayers of the inner sub-membrane are in direct contact with each other, and on either side of the two middle microlayers or nanolayers of the inner sub-membrane is one microlayer or nanolayer that comprises, consists of, or consists essentially of polypropylene.

189. 178. The multilayer microporous membrane or film of claim 177, wherein the microlayers or nanolayers all have the same thickness.

190. 178. The multilayer microporous membrane or film of claim 177, wherein the microlayers or nanolayers do not all have the same thickness.

191. 178. The multilayer microporous membrane or film of claim 177, wherein each of said sub-membranes is formed by coextrusion.

192. 192. The multilayer microporous membrane or film of claim 191, wherein each of the coextruded submembranes is laminated to at least one other coextruded submembrane to form the multilayer microporous membrane.

193. 178. The multilayer microporous membrane or film of claim 177, wherein the membrane or film comprises 10 to 35 weight percent polyethylene, based on the total weight of the membrane or film.

194. 200. The multilayer microporous membrane or film of claim 193, wherein the membrane or film comprises 15 to 25 weight percent polyethylene, based on the total weight of the membrane or film.

195. A battery separator comprising, consisting of, or consisting essentially of at least one multilayer microporous membrane or film according to any one of claims 1-194.

196. 196. The battery separator of claim 195, wherein said membrane or film is coated on one or two sides thereof.

197. 200. The battery separator of claim 196, wherein said membrane or film is coated on one side.

198. 200. The battery separator of claim 196, wherein said membrane or film is coated on two sides.

199. 200. The battery separator of any one of claims 196-198, wherein the coating is a ceramic coating comprising, consisting of, or consisting essentially of inorganic or organic particles and a polymeric binder.

200. 200. A battery comprising the battery separator of any one of claims 195 to 199.

201. A vehicle or device comprising the battery of claim 200.

202. A textile comprising, consisting of, or consisting essentially of at least one multilayer microporous membrane or film according to any one of claims 1 to 194.

203. A textile comprising, consisting of, or consisting essentially of at least one multilayer microporous membrane or film according to any one of claims 1 to 194, and a nonwoven or woven fabric.

204. The fabric of claim 203, wherein the nonwoven or woven fabric is attached to the multi-layer microporous membrane.

205. 1. A method for making a multi-layer microporous membrane containing an additive in at least one layer, comprising: co-extruding the additive-containing polymer mixture with at least one other polymer mixture to form a co-extruded precursor film; or extruding the polymer mixture containing the additive to form a co-extruded precursor film and laminating the co-extruded precursor film to at least one other film; The method comprising:

206. Co-extruding the additive-containing polymer mixture with at least one other polymer mixture; 206. The method of claim 205, comprising forming a coextruded precursor film.

207. 206. The method of claim 205, comprising extruding a polymer mixture containing the additive to form a co-extruded precursor film, and laminating the co-extruded precursor film to at least one other film.

208. 208. The method of claim 207, wherein laminating comprises application of at least one of heat, pressure, or a combination thereof.

209. A machine learning test described herein for characterizing a multilayer microporous film comprising two or more layers and polyethylene and / or polypropylene in one or more of the layers.

210. In some embodiments, the following is met: W Ｔ x ' ≧0.0 or W Ｔ x ' ≧2.0 PP:w Ｔ x'≧-1.5w Ｔ x'≧0.5w Ｔ x'≧1.5 PE:w Ｔ x'≧-2.07 Ｔ x'≧0.07 Ｔ x'≧2.0 210. The machine learning test of claim 209.

211. A method for determining whether a given microporous membrane is a multilayer microporous membrane, the method comprising the steps shown in FIG.

31.

212. New or improved methods for testing, quantifying, characterizing, and / or analyzing microporous polymeric membranes, separator membranes, separators, battery separators, and the like.

213. A multi-layer microporous membrane that exhibits an increase in puncture average (g) when tested at high puncture rates above 25 mm / min compared to the puncture average (g) tested at 25 mm / min.

214. 214. The multi-layer microporous membrane of claim 213, wherein the puncture average is at least about 20 g higher at a puncture rate of 100 mm / min than at 25 mm / min.

215. 214. The multi-layer microporous membrane of claim 213, wherein the puncture average is at least about 30 g higher at a puncture rate of 100 mm / min than at 25 mm / min.

216. 214. The multi-layer microporous membrane of claim 213, wherein the puncture average is at least about 40 g higher at a puncture rate of 100 mm / min than at 25 mm / min.

217. 217. The multilayer microporous membrane of any one of claims 213 to 216, wherein the puncture average at a puncture speed of 25 mm / min is greater than 250 g.

218. 218. The multi-layer microporous membrane of claim 217, having a thickness between 14 and 30 microns.

219. 217. The multilayer microporous membrane of any one of claims 213 to 216, wherein the puncture average at a puncture speed of 25 mm / min is greater than 275 g.

220. 220. The multi-layer microporous membrane of claim 219, having a thickness between 14 and 30 microns.

221. 217. The multilayer microporous membrane of any one of claims 213 to 216, wherein the puncture average at a puncture speed of 25 mm / min is greater than 300 g.

222. 222. The multi-layer microporous membrane of claim 221, having a thickness between 14 and 30 microns.

223. 217. The multilayer microporous membrane of any one of claims 213 to 216, wherein the puncture average at a puncture speed of 25 mm / min is greater than 325 g.

224. 224. The multi-layer microporous membrane of claim 223, having a thickness between 14 and 30 microns.

225. 217. The multilayer microporous membrane of any one of claims 213 to 216, wherein the puncture average at a puncture speed of 25 mm / min is greater than 350 g.

226. 226. The multi-layer microporous membrane of claim 225, having a thickness between 14 and 30 microns.

227. 1. A microporous membrane formed by a collapsed bubble method, the microporous membrane having a thickness of less than 14 microns and a puncture strength of greater than 200 g.

228. The microporous membrane of claim 227, having a thickness of 6 microns to 12 microns.

229. 228. The microporous membrane of claim 227, having a thickness of about 10 microns.

230. 228. The microporous membrane of claim 227, wherein the puncture strength is 210 g or greater.

231. 228. The microporous membrane of claim 227, wherein the puncture strength is 220 g or greater.

232. 228. The microporous membrane of claim 227, wherein the puncture strength is 230 g or greater.

233. 228. The microporous membrane of claim 227, wherein the puncture strength is 240 g or greater.

234. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PP / PP / PE / PE / PP / PP, the structure comprising co-extruded PP / PP / PE formed by collapsing air bubbles.

235. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PP / PE / PE / PE / PE / PP, the structure comprising co-extruded PP / PE / PE formed by collapsing air bubbles.

236. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PP / PP / PP / PP, the structure comprising co-extruded PP / PP formed by collapsing air bubbles.

237. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PE / PE / PE / PE, the structure comprising co-extruded PE / PE formed by collapsing air bubbles.

238. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PP / PE / PE / PP, the structure comprising co-extruded PP / PE formed by collapsing air bubbles.

239. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises a structure PE / PP / PP / PE, the structure comprising co-extruded PE / PP formed by collapsing air bubbles.

240. 228. The microporous membrane of claim 227, wherein the microporous membrane comprises the structure PE / PP / PP / PP / PP / PE, the structure comprising co-extruded PE / PP / PP formed by collapsing air bubbles.

241. 228. The microporous membrane of claim 227, wherein the microporous membrane has the structure PP / PE / PP / PE / PE / PP / PE / PP, the structure comprising co-extruded PP / PE / PP / PE formed by collapsing air bubbles.

242. 228. The microporous membrane of any one of claims 227, wherein the cross-sectional SEM shows the discernible interface formed when the bubbles collapse, an example of which is shown in this high magnification cross-sectional SEM.

243. 228. The microporous membrane of claim 227, wherein the microporous membrane has a Gurley of less than 250.

244. 244. The microporous membrane of claim 243, wherein the microporous membrane has a Gurley of less than 225.

245. 245. The microporous membrane of claim 244, wherein the microporous membrane has a Gurley of less than 200.

246. 246. The microporous membrane of claim 245, wherein the microporous membrane has a Gurley of less than 190.

247. 247. The microporous membrane of claim 246, wherein the microporous membrane has a Gurley of less than 180.

248. 248. The microporous membrane of claim 247, wherein the microporous membrane has a Gurley of less than 175.

249. 228. The microporous membrane of claim 227, comprising polyethylene having a melt flow rate of 0.1 to 10 g / min.

250. 228. The microporous membrane of claim 227, wherein at least one layer of the membrane comprises polyethylene and is at least 1.75 microns thick.

251. 228. The microporous membrane of claim 227, wherein at least one layer of the membrane comprises polyethylene and is at least 2 microns thick.

252. 228. The microporous membrane of claim 227, wherein at least one layer of the membrane comprises polyethylene and is less than 2 microns in thickness.

253. 228. The microporous membrane of claim 227, comprising polypropylene having a melt flow rate of 0.01 to 10 g / 10 min as measured by ASTM D1238-13 and / or ISO 1133-1:2011.

254. 228. The microporous membrane of claim 227, comprising polypropylene having a melt flow rate of 0.1 to 5 g / 10 min as measured by ASTM D1238-13 and / or ISO 1133-1:2011.

255. 228. The microporous membrane of claim 227, comprising polypropylene having a melt flow rate of 0.01 to 2.5 g / 10 min as measured by ASTM D1238-13 and / or ISO 1133-1:2011.

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