Battery separator, coated battery separator, battery and relevant method

Abstract

To provide a simple and good method for improving bonding to a PP-containing separator of a coating or a film layer, which contains a polyaramid material.SOLUTION: There is provided new or improved fine porous single layer, two-layer, three-layer or multilayer film, separator film, separator, or coated separator. Preferably, the film is produced from at least one resin or polymer, and at least one additive. The additive may contain at least one material for improving bonding to a coating containing a polyaramid-containing coating and a PCS coating, or a different material such as a metal surface including an electrode surface, of the fine porous film. The improvement of bonding is based on comparison with a similar fine porous film which does not contain at least one additive.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] A new or improved microporous monolayer, bilayer, trilayer or multilayer membrane, separator membrane, separator or coated separator is disclosed. The membrane is preferably made from at least one resin or polymer and at least one additive. The additive may include at least one material that improves adhesion of the microporous membrane to a coating, preferably a polyaramid-containing coating, or to a different material, such as a metal surface. The improved adhesion is based on a comparison to a similar microporous membrane that does not include the at least one additive. In some preferred embodiments, the at least one additive may include, consist of, or consist essentially of a functional polymer or a combination of a functional polymer and an elastomer. In some embodiments, the functional group of the functional polymer may be maleic anhydride (MAH). Also disclosed is a battery separator or coated separator that includes the new or improved microporous membrane. The battery separator may include a microporous membrane coated with a polyaramid-containing coating. Also disclosed are new or improved separators, composites, batteries, lithium ion secondary batteries, and / or vehicles or devices including the separators, composites, or batteries. [Background technology]

[0002] The battery separator may be formed by a dry manufacturing process, including the Celgard® dry stretch process. Some dry battery separators may be either a monolayer polypropylene (PP) as described in International Patent Application No. PCT / US17 / 61277, a trilayer film consisting of PP / PE / PP, or a multilayer film, such as, for example, (PP)(PP)(PP) / (PE)(PE)(PE) / (PP)(PP)(PP). Other multilayer structures are disclosed in International Patent Application No. PCT / US17 / 61277, which is incorporated herein by reference in its entirety. PP is generally used as the outermost layer material of the battery separator due, among other things, to its oxidation resistance, which provides excellent cycling performance. In trilayer and multilayer structures, PE can be used in the inner layer(s) to, among other things, provide fast shutdown capability.

[0003] Many of today's high energy lithium battery separators are coated with a ceramic coating, which may include organic or inorganic particles and a binder, typically a polymeric binder. Ceramic coatings for battery separators were first disclosed in U.S. Pat. No. 6,432,586, the entire contents of which are incorporated herein by reference.

[0004] Polyaramid materials, which are commonly used as binders in ceramic and other types of coatings, are known not to bond well with certain polyolefins (POs), such as polypropylene (PP), which is a material commonly used in the outer layer(s) of mono-ply and tri- and multi-ply battery separators, as discussed above. Some representative polyaramids are Kevlar®, Twaron®, New Star®, and Teijin conex. There are limited known methods to improve adhesion between PP-containing layers and coatings that include polyaramid materials, but these limited known methods require additional processing steps. For example, an additional surface treatment step may be performed prior to coating. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Patent Application No. PCT / US17 / 61277 [Patent Document 2] U.S. Patent No. 6,432,586 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, simpler and better methods of improving the adhesion of coatings, including those containing polyaramid materials, to PP-containing separator or membrane layers are desirable. [Means for solving the problem]

[0007] According to at least selected embodiments, the present disclosure or invention may address prior problems, needs or issues and / or provide new or improved microporous monolayer, bilayer, trilayer or multilayer membranes, separator membranes, separators, coated separators as disclosed. The membranes are preferably made from at least one resin or polymer and at least one additive. The additive may include at least one material that improves adhesion of the microporous membrane to a coating, including a polyaramid-containing coating, an aramid coating, another polymer coating, or a different material, such as a metal surface. The improved adhesion is based on a comparison to a similar microporous membrane that does not include the at least one additive. In some preferred embodiments, the at least one additive may include, consist of, or consist essentially of a functional polymer or a combination of a functional polymer and an elastomer. In some embodiments, the functional group of the functional polymer may be maleic anhydride (MAH). In some embodiments, the additive may improve other properties of the microporous membrane. In these embodiments, the additive may be a resin having both olefinic and polar moieties. For example, in some embodiments, the additive may be at least one of an acid copolymer, an ionomer, and a maleic anhydride modified PP or PE homopolymer and / or copolymer resin. Also disclosed are battery separators or coated separators comprising the new or improved microporous membranes. The battery separator may comprise a microporous membrane coated with a coating, such as a polyaramid-containing coating. Also disclosed are new or improved separators, composites, batteries, lithium ion secondary batteries, and / or vehicles or devices comprising the separators, composites, or batteries.

[0008] Any microporous membrane described herein may be used in or may be a textile. For example, a textile may include, consist of, or consist essentially of any microporous membrane described herein. In some embodiments, a laminated textile is described that includes at least one microporous membrane described herein. In some embodiments, the laminate may include one or more microporous membranes described herein. In some embodiments, the laminate may include one or more microporous membranes described herein and another woven, nonwoven, knit, coating, and / or porous or microporous layer. In some embodiments, the textile or laminated textile disclosed herein may be used in clothing such as jackets, pants, shirts, hats, socks, underwear, gloves, or shorts. In some embodiments, the textile or laminated textile disclosed herein may be used to form outdoor items such as tents, backpacks, or tarps.

[0009] In other embodiments, a laminate or composite membrane, material, or separator may include one or more microporous membranes described herein and another woven, nonwoven, knit, coating, and / or porous or microporous layer.

[0010] In some other embodiments, the single membrane or separator or the laminate or composite membrane, material or separator may be any desired thickness, design, pattern, etc. Depending on the application, the material may be embossed, calendared, coated, treated and / or further processed. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a table containing data collected for several embodiments described herein. [Diagram 2] FIG. 2 is a table containing data collected for several embodiments described herein. [Diagram 3] FIG. 3 is a table containing data collected for several embodiments described herein. [Figure 4] FIG. 4 is a table containing data collected for several embodiments described herein. [Diagram 5] FIG. 5 is a table containing data collected for several embodiments described herein. [Figure 6] FIG. 6 is an SEM image of an embodiment described herein. [Figure 7] FIG. 7 is an SEM image of an embodiment described herein. [Figure 8] FIG. 8 is an SEM image of an embodiment described herein. [Figure 9] 9A and 9B are SEM images of a comparative example. [Figure 10] 10A and 10B are SEM images of embodiments described herein. [Figure 11] 11A and 11B are SEM images of embodiments described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Described herein are new or improved microporous membranes, which may be used as or in battery separators, for example, for lithium ion batteries. Some of the microporous membranes described herein have improved adhesion to coatings, metals and / or polyaramid-material-containing coatings, as compared to conventional monolayer polypropylene (PP), trilayer films consisting of PP / PE / PP, or multilayer films (two or more layers), such as (PP)(PP)(PP) / (PE)(PE) / (PP)(PP)(PP), as described, for example, in International Patent Application No. PCT / US17 / 61277.

[0013] In one aspect, described herein is a microporous membrane made from at least one polymer or resin and at least one additive. At least one surface of the microporous membrane exhibits higher adhesion or bond strength to a coating, including a coating that includes polyaramid (or poly-aramid or aramid), or to a metal surface, and to another microporous membrane that is otherwise identical except that the other microporous membrane does not include the at least one additive. In some embodiments, both surfaces of the microporous membrane exhibit higher adhesion strength to a coating, including a coating that includes polyaramid, or to a metal surface, and to another microporous membrane that is otherwise identical except that the other microporous membrane does not include the at least one additive. The high adhesion of the surface of the microporous membrane that includes the at least one additive is achieved without coating, treating, or otherwise increasing adhesion to the surface(s) of the microporous membrane.

[0014] In some embodiments, the at least one polymer used in the microporous membrane is polypropylene or another polymer that is immiscible with polyaramid. Other polymers, including polymers that are immiscible, miscible, or partially miscible with polyaramid, may be used in addition to the polypropylene or another polymer that is immiscible with polyaramid. The polypropylene may be a homopolymer polypropylene, a copolymer polypropylene, or a mixture thereof. , terpolymer polypropylene, and combinations thereof.

[0015] In some embodiments, the additive is a compatibilizer for polypropylene and any polymer that is immiscible with polypropylene. For example, a compatibilizer may be used to stabilize a blend of polypropylene and any polymer that is immiscible with polypropylene. In some embodiments, the additive comprises a functional polymer. For example, a maleic anhydride modified polyolefin may be used. Exemplary functional polyolefins may be selected from the group consisting of maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, and combinations thereof. Specific examples of maleic anhydride modified polyolefins include maleic anhydride modified high density polyethylene (MA-HDPE), maleic anhydride modified copolymer polypropylene (MA-Co-PP), and maleic anhydride modified homopolymer polypropylene (MA-Homo-PP).

[0016] In some embodiments, the additive may be present in an amount of 0.05-20 wt%, 0.5-15 wt%, 1-10 wt%, or 1-5 wt%, based on the total weight of the membrane. In some embodiments, the microporous membrane is a monolayer, bilayer, trilayer, or multilayer membrane. In some preferred embodiments, the microporous membrane is a polyolefin monolayer, bilayer, trilayer, or multilayer membrane, such as a PP and / or PE membrane. In some particularly preferred embodiments, the microporous membrane is a polyolefin monolayer, bilayer, trilayer, or multilayer membrane, with at least a PP outer layer or surface having at least one adhesion promoting additive or polymer.

[0017] In a bilayer film, one or both of the layers of the bilayer film may include the at least one additive. In a three-layer embodiment, one or both of the outermost layers may include the at least one additive, and in some three-layer embodiments, only the inner layer or one or both of the outermost layers may include the at least one additive. In a multilayer film, one or both of the outermost layers may include the at least one additive. In some multilayer embodiments, at least one inner layer or at least one inner layer and one or both outermost layers may include the at least one additive. In some multilayer embodiments, all of the inner layers or all of the inner layers and one or both outermost layers may include the at least one additive.

[0018] In some preferred embodiments, the additive is present in an amount of up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%, based on the weight of the layer or layers present.

[0019] In some preferred embodiments, both outermost layers of the membrane exhibit improved adhesion and include the at least one additive. In other embodiments, at least one surface exhibits at least one of the following, compared to a microporous membrane made from the at least one polymer but not containing any additive: reduced pin removal force, more controlled pore size, improved electrolyte wetting, improved ion capture, enhanced toughness or durability, and combinations thereof. These properties may be caused by the at least one additive or another additive resulting in improved adhesion. The at least one surface may also exhibit at least one of the above properties in addition to or instead of improved adhesion to a coating, including a polyaramid-containing coating, or a metal surface. In some embodiments, one surface of the membrane exhibits improved adhesion to a coating, including a polyaramid-containing coating, or a metal surface, and the other surface of the membrane exhibits one or more of the above properties, such as improved toughness or durability. In some embodiments, one or both surfaces of the membrane exhibit at least one of the above properties, such as improved adhesion to a coating, including a polyaramid-containing coating, or a metal surface. The composition may exhibit one or more of the properties described above, such as improved adhesion to the surface and improved toughness or durability.

[0020] In some embodiments, at least one surface of the membrane exhibits at least reduced pin removal force or at least reduced pin removal force and improved adhesion with coatings or metal surfaces, including polyaramid-containing coatings. In such embodiments, the microporous membrane may also include at least one additive, including at least one lubricant, which may provide reduced pin removal force. The lubricant may be amphiphilic. The lubricant may also be a fatty acid salt. Exemplary fatty acid salts may include lithium stearate, sodium stearate, and potassium stearate, and combinations thereof. In some embodiments, the lubricant may be a compound containing one or more siloxy functional groups, including siloxane or polysiloxane. In some embodiments, the lubricant may be an ultra-high molecular weight polysiloxane.

[0021] In some embodiments, at least one surface of the membrane exhibits more controlled pore size or at least more controlled pore size and improved adhesion to coatings or metal surfaces, including polyaramid-containing coatings. In such embodiments, the microporous membrane may also include at least one additive comprising a homopolymer, copolymer, or terpolymer having a different molecular weight than the at least one polymer or resin from which the microporous membrane is made.

[0022] In some embodiments, at least one surface of the membrane exhibits improved electrolyte wetting or at least improved electrolyte wetting and improved adhesion to coatings, including polyaramid-containing coatings.

[0023] In some embodiments, at least one surface of the membrane exhibits improved ion trapping or at least improved ion trapping and improved adhesion to coatings, including polyaramid-containing coatings. For example, ionomer additives may improve ion trapping.

[0024] In some embodiments, at least one surface of the membrane exhibits enhanced durability or toughness or at least enhanced durability and improved adhesion to coatings, including polyaramid-containing coatings. Enhanced toughness may mean enhanced tensile strength in some embodiments. In such embodiments, the microporous membrane may also include at least one additive including an ionomeric resin that may provide increased toughness or increased tensile strength properties. In such embodiments, the additive comprises, consists of, or consists essentially of an ionomer. An ionomer is a copolymer that includes both ion-containing and non-ionic repeat groups, as understood by one of ordinary skill in the art. In some cases, the ion-containing repeat groups may account for 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. Examples of commercially available ionomers include Surlyn® sold by DuPont™, Primacor™ available from SK Global Chemical, Eltex® available from Ineos, and Aquavion® available from Solvay.

[0025] In some embodiments, the microporous membranes described herein are coated on at least one side with a polyaramid-containing coating. Preferably, a polyaramid-containing coating is coated on the side or both sides of the membrane that exhibits improved adhesion to the polyaramid-containing coating. In some embodiments, the polyaramid-containing coating is coated on the side or both sides of the membrane that exhibits improved adhesion to the polyaramid-containing coating. The coating also includes at least one of an organic filler, an inorganic filler, and combinations thereof. In some embodiments, the microporous membranes described herein are coated with a polymeric coating, where the polymeric coating can include, consist of, or consist essentially of a polymer, e.g., an acrylic polymer.

[0026] In some embodiments, at least one side of the microporous membrane described herein is in direct contact with a metal surface. Preferably, the side of the membrane that exhibits improved adhesion to a metal surface is in contact with a metal surface. In some embodiments, both sides of the membrane are in direct contact with a metal surface or one side is in contact with a metal surface and one side is in contact with a coating, such as a polyaramid-containing coating.

[0027] In some embodiments, the at least one surface may be coated, treated, or otherwise modified to improve strength even further, for example, the at least one surface may be corona treated or coated with a PE and / or latex coating.

[0028] In another aspect, a microporous membrane or membrane layer is disclosed that is made from at least one polymer or resin and at least one additive that performs at least one of the following functions: (1) enhances adhesion between a coating layer and at least one surface of the microporous membrane, (2) enhances adhesion between a metal surface and at least one surface of the microporous membrane, (3) reduces pin removal on at least one surface of the microporous membrane, (4) enhances wettability with an electrolyte on at least one surface of the microporous membrane, (5) enhances ion trapping on at least one surface of the microporous membrane, (6) enhances toughness or tensile strength on at least one surface of the microporous membrane, (7) controls pore size on at least one surface of the microporous membrane, (8) reduces static on at least one surface of the microporous membrane, (9) enhances puncture strength, and (10) enhances ion transport across the membrane. In some embodiments, one additive performs 1, 2, 3, 4, 5, 6, 7, 8, 9, or all 10 of these functions. In some embodiments, different additives are added that perform 1, 2, 3, 4, 5, 6, 7, 8, 9, or all 10 of these functions.

[0029] In some embodiments, the additive enhances adhesion between a coating layer, such as a ceramic coating or a polymeric coating layer, and at least one surface of the microporous membrane. The coating layer is, in some preferred embodiments, a polyaramid-containing coating layer. In some such embodiments, the additive is a functional polymer that enhances adhesion between a coating layer and at least one surface of the microporous membrane. Exemplary functional polymers include anhydride-modified polyethylene, anhydride-modified polypropylene, and combinations thereof. Specific examples of maleic anhydride-modified polyolefins include maleic anhydride-modified high density polyethylene (MA-HDPE), maleic anhydride-modified copolymer polypropylene (MA-Co-PP), and maleic anhydride-modified homopolymer polypropylene (MA-Homo-PP).

[0030] In some embodiments, the additive enhances adhesion between a metal surface and at least one surface of the microporous membrane. In some embodiments, the metal surface is a metal electrode. In some such embodiments, the additive is a functional polymer that enhances adhesion between a coating layer and at least one surface of the microporous membrane. Exemplary functional polymers include anhydride-modified polyethylene, anhydride-modified polypropylene, and combinations thereof. Specific examples of maleic anhydride-modified polyolefins include maleic anhydride-modified high density polyethylene (MA-HDPE), maleic anhydride-modified copolymer polypropylene (PCP), and combinations thereof. (MA-Co-PP), and maleic anhydride modified homopolymer polypropylene (MA-Homo-PP).

[0031] The amount of functional polymer may range from 1 to 100% by weight based on the weight of the membrane or based on the weight of the layer to which it is added.

[0032] The functionalization of functional polymers may vary. Functionalization is the amount of functional groups (e.g. MAH groups) present in a given weight or amount of polymer. Due to this variation in functionalization of functional polymers, it is important to consider the amount of functional groups, and not just the amount of functional polymer added to form the microporous membrane. In a preferred embodiment, the amount of functional groups is between 0.05 and 5 wt.% based on the total weight of the microporous membrane or based on the total weight of the layer of the membrane to which the functional polymer (and therefore the functional group) is added. In a single layer membrane, the amount of functional groups is between 0.05 and 5 wt.% based on the total weight of the microporous membrane or based on the total weight of the layer of the membrane to which the functional polymer (and therefore the functional group) is added, and is the same. In some embodiments, the amount is 0.1 to 5 wt%, 0.2 to 5 wt%, 0.5 to 5 wt%, 1 to 5 wt%, 1.5 to 5 wt%, 2 to 5 wt%, 2.5 to 5 wt%, 3 to 5 wt%, 3.5 to 5 wt%, 4 to 5 wt%, or 4.5 to 5 wt%, based on the total weight of the microporous membrane or based on the total weight of the layer of the membrane to which the functional polymer (and therefore functional group) is added.

[0033] In some embodiments, the additive reduces pin removal of at least one surface of the microporous membrane. In some such embodiments, the additive comprises a lubricant. The lubricants or lubricants described herein are not very limited. As understood by one of ordinary skill in the art, lubricants are compounds that act to reduce friction between various different surfaces, including the following: polymer:polymer, polymer:metal, polymer:organic material, polymer:inorganic material. Specific examples of the lubricants or lubricants described herein include compounds that contain siloxy functional groups, including siloxanes and polysiloxanes, and fatty acid salts, including metal stearates.

[0034] In some embodiments, the additive may be a surface friction modifier that may increase or decrease the surface friction of at least one surface of the microporous membrane. For example, the additive may be a blocking agent, an anti-blocking agent (silica, diatomaceous earth, calcium carbonate, or a combination thereof), a slip agent, or an anti-slip agent.

[0035] Compounds containing 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more siloxy groups may be used as lubricants as described herein. As will be understood by those skilled in the art, siloxanes are a class of molecules with a backbone of alternating silicon (Si) and oxygen (O) atoms, where each silicon atom can have a hydrogen (H) bonded to it, or a saturated or unsaturated carbon group, e.g., -CH3 or C2H5. Polysiloxanes are polymerized siloxanes, usually with a high molecular weight. In some preferred embodiments described herein, the polysiloxane may be a high molecular weight polysiloxane, and in some even more preferred cases, an ultra-high molecular weight polysiloxane. In some embodiments, the high molecular weight and ultra-high molecular weight polysiloxanes may have a weight average molecular weight ranging from 500,000 to 1,000,000.

[0036] The fatty acid salt described herein is not particularly limited and may be any fatty acid salt that acts as a lubricant. The fatty acid of the fatty acid salt may be a fatty acid having between 12 and 22 carbon atoms. For example, the fatty acid metal salt may be a fatty acid having lauric acid, myristic acid, palladium acid, glycerin, glycerol ... The metal may be selected from the group consisting of nitic 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 is an alkali metal 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.

[0037] 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.

[0038] In some preferred embodiments described herein, the lubricating oils comprising 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. Fatty acid salts such as lithium stearate (melting point 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 the present application have found that calcium stearate is less ideal from a process standpoint than other fatty acid metal salts, such as metal stearates, which have higher melting points. In particular, it has been found that calcium stearate cannot be added in amounts greater than 800 ppm without causing what is referred to as a "snowing effect" where the wax separates and reaches everywhere during the hot extrusion process. Without wishing to be bound by any theory, it is believed that the use of fatty acid metal salts with melting points higher than the hot extrusion temperature can solve this "snowing problem". Fatty acid salts with higher melting points than calcium stearate, particularly those with melting points above 200°C, may be incorporated in amounts of 1% or greater than 1,000 ppm without producing "snowing". Amounts of 1% or greater have been found to be important for achieving desirable properties such as improved wettability and improved pin removal. In some preferred embodiments, amounts of 1-10%, 1-9%, 1-8%, 1-7%, 1-6%, 1-5%, 1-4%, 1-3%, or 1-2% may be used.

[0039] In some preferred embodiments, a PE and / or latex coating may be applied at some point to reduce pin removal forces.

[0040] In some embodiments, the at least one additive enhances wettability with an electrolyte on at least one side of the microporous membrane. In such embodiments, the additive may be or include a functional polymer, including anhydride-modified polyethylene, anhydride-modified polypropylene, and combinations thereof, as described herein. In some embodiments, the additive may be or include an ionomer.

[0041] In some embodiments, the at least one additive enhances ion trapping on at least one surface of the microporous membrane.

[0042] In some embodiments, the at least one additive enhances the toughness or tensile strength of at least one surface of the microporous membrane.

[0043] In some embodiments, the at least one additive controls the pore size of at least one surface of the microporous membrane, hi some such embodiments, the at least one additive comprises, consists of, or consists essentially of a homopolymer, copolymer, or terpolymer having a different molecular weight than the polymer or resin from which the microporous membrane is made.

[0044] In some embodiments, the at least one additive reduces static electricity on at least one surface of the microporous membrane.

[0045] In some embodiments, the additive may be at least one selected from acid copolymers (e.g., copolymers of ethylene (E) and methacrylic acid (MAA) or acrylic acid (AA), such as, for example, Nucrel™ from DuPont), ionomers (e.g., Surlyn™ from DuPont, Primacor™ available from SK Global Chemical, Eltex® available from Ineos, Aquavion® available from Solvay), maleic anhydride modified PP or PE homopolymer and / or copolymer resin(s), lubricating oil, and / or other typical additives or fillers, and combinations thereof.

[0046] In some embodiments, the microporous membrane is a monolayer, bilayer, trilayer, or multilayer microporous membrane. The term "layer" includes a monoextruded layer having a thickness of 0.1 to 35 microns. As will be understood by those skilled in the art, a monoextruded layer is a layer extruded by itself without any other. Also, the layers of a coextruded bi-layer, tri-layer, or multi-layer membrane are each considered to be a "layer". The number of layers in a coextruded bi-layer is 2, the number of layers in a coextruded tri-layer is 3, and the number of layers in a coextruded multi-layer film is 2 or more, preferably 3 or more, or 4 or more. The exact number of layers in a bi-layer, tri-layer, or multi-layer coextruded film is determined by the die design, not necessarily the materials that are coextruded to form the coextruded film. For example, a coextruded bi-, tri-, or multi-layer film may be formed using the same material that forms each of the 2, 3, or 4 or more layers, and these layers are still considered to be separate layers even if each is made of the same material. The exact number is again determined by the die design.

[0047] A monolayer microporous membrane may consist of a single monoextruded layer. A bilayer microporous membrane may consist of two coextruded layers or two monoextruded layers laminated together. A trilayer microporous membrane may consist of three coextruded layers, three monoextruded layers laminated together or two coextruded layers and one monoextruded layer. A multilayer may consist of, for example, four or more coextruded layers, two or more coextruded layers laminated with two or more other coextruded layers, two or more coextruded layers laminated with two other sets of two or more coextruded layers or three coextruded layers laminated to a monoextruded layer.

[0048] In some embodiments, the microporous membrane is made of polyolefin resins, including polyethylene, polypropylene, and mixtures thereof and combinations thereof. In some embodiments, the microporous membrane is a monolayer membrane made of polyolefin resins. For example, it may be made of polyethylene, polypropylene, or mixtures thereof. In some preferred embodiments, the monolayer membrane comprises a number of polypropylenes. In some embodiments, the microporous membrane is a bilayer membrane, where one or both layers are made of polyolefins. In some preferred embodiments, at least one layer of the bilayer is made of a number of polypropylenes. In some embodiments, the microporous membrane is a trilayer membrane, where at least one of the layers is made of a number of polyolefins. In some preferred embodiments, at least one or both outermost layers of the trilayer comprise a number of polypropylenes. In some embodiments, the microporous membrane is a multilayer membrane, where at least one layer is made of polyolefins. In some preferred embodiments, at least a number of the outermost layers of the multilayer embodiment comprise a number of polypropylenes.

[0049] In some embodiments, the at least one additive enhances adhesion between a coating layer or metal layer and at least one surface of the microporous membrane and reduces pin removal on a different surface of the microporous membrane. and reduce pin removal force, and in some embodiments, different additives provide these different properties.

[0050] In another embodiment, a multi-layer microporous membrane is described as including at least one additive in one or both outermost layers of the membrane, the additive performing at least one of the following functions: (1) enhancing adhesion between a coating layer and at least one surface of the microporous membrane, (2) enhancing adhesion between a metal surface and at least one surface of the microporous membrane, (3) reducing pin removal on at least one surface of the microporous membrane, (4) enhancing wettability with an electrolyte on at least one surface of the microporous membrane, (5) enhancing ion trapping on at least one surface of the microporous membrane, (6) enhancing toughness or tensile strength on at least one surface of the microporous membrane, (7) controlling pore size on at least one surface of the microporous membrane, (8) reducing static electricity on at least one surface of the microporous membrane, (9) enhancing puncture strength, and (10) enhancing ion transport across the membrane. In some embodiments, one additive performs 1, 2, 3, 4, 5, 6, 7, 8, 9, or all 10 of these functions. In some embodiments, different additives are added that perform 1, 2, 3, 4, 5, 6, 7, 8, 9, or all 10 of these functions.

[0051] In some embodiments where both outermost layers include at least one additive, the additives may be the same or different. In some embodiments, the inner layers of the multilayer film may also include at least one additive. In some embodiments where additives may be lost from the film over time, such as by evaporation or decomposition of the additive in the outer or outermost layer, the additive in the inner layer may migrate to the outer layers and replenish the additive lost from the outer or outermost layer.

[0052] In some multi-layer embodiments, the outermost layer may have a thickness of 01 to 20 microns, 1 to 15 microns, 2 to 10 microns, 3 to 5 microns, 0.1 to 5 microns, 0.1 to 3 microns, 0.1 to 2.5 microns, 0.1 to 2 microns.

[0053] The microporous membranes described herein, including multilayer embodiments, may have a thickness of 1-60 microns, 1-50 microns, 1-40 microns, 1-30 microns, 1-25 microns, 1-20 microns, 1-15 microns, 1-10 microns, or 1-5 microns. In some cases, the membranes may be much thinner than 5 microns or much thicker than 30 microns. However, for purposes of use in lithium ion batteries, thinner membranes are generally preferred, particularly 20 microns or less, 15 microns or less, 12 microns or less, or 10 microns or less.

[0054] In another aspect, a battery separator is described that includes any of the monolayer, bilayer, trilayer, or multilayer microporous membranes described herein. In some preferred embodiments, the microporous membrane may be coated with a coating that includes a polyaramid. In some further preferred embodiments, the coating may be a ceramic polyaramid-containing coating that further includes inorganic particles, organic particles, or a combination thereof.

[0055] In another aspect, a lithium ion secondary battery is described that includes a battery separator as described herein.

[0056] In another aspect, a composite is described that includes a battery separator as described herein in direct contact with at least one electrode of a lithium ion secondary battery. In some embodiments, the separator may directly contact two electrodes for a lithium ion secondary battery. In other embodiments, the separator is used in a battery, lithium battery, lithium secondary battery, capacitor, supercapacitor, hybrid battery / capacitor, cell, electric It may be used in chemical cells, systems, modules, packs and / or the like.

[0057] In another aspect, a vehicle or device is described that includes a battery separator, lithium ion secondary battery, capacitor, or composite described herein.

[0058] Also, any porous or microporous membrane described herein may optionally be used or may be in textiles, filters, HVAC units, fuel cells, PEMs, humidity control layers, transdermal patches, and / or the like. For example, a textile may include, consist of, or consist essentially of any microporous membrane described herein. In some embodiments, a laminated textile is described that includes at least one microporous membrane described herein. In some embodiments, the laminate may include one or more microporous membranes described herein. In some embodiments, the laminate may include one or more microporous membranes described herein and another woven, nonwoven, knit, coating, and / or porous or microporous layer. In some embodiments, the textile or laminated textile disclosed herein may be used in garments such as jackets, pants, shirts, hats, socks, underwear, gloves, or shorts. In some embodiments, the textile or laminated textile disclosed herein may be used to form outdoor items such as tents, backpacks, or tarps.

[0059] In other embodiments, a laminate or composite membrane, material or separator may include one or more microporous membranes described herein and additional woven, nonwoven, knit, coating and / or porous or microporous layers.

[0060] In some other embodiments, the single membrane or separator or laminate or composite membrane, material or separator may be embossed, calendared, coated, treated and / or further processed depending on the desired end use, thickness, design, pattern, etc. EXAMPLES

[0061] When an MAH functional polymer was added, certain samples were prepared so that the functional group content (MAH content) was 0.05 to 5.0 wt % based on the weight of the layer to which the functional polymer was added.

[0062] Example 1 - To form Example 1, polypropylene and 5% maleic anhydride modified high density polyethylene were extruded (monoextrusion) to form a single layer thin film precursor. No solvent was used. The extruded precursor was then stretched to form pores. Data for Example 1 can be found in Table 1.

[0063] Note that the same polypropylene was used in each example and comparative example, what was varied was the additive (or lack thereof).

[0064] Example 2(a) - Example 2(a) was made in a similar manner to Example 1, except that 10% maleic anhydride modified homo-PP was added instead of the 5% maleic anhydride modified HDPE. The data for Example 2(a) is found in Tables 1-4 below. An SEM of Example 2(a) is also shown below. This is the same modified homo-PP used in Examples 2(b), 4, and 6-13.

[0065] Example 2(b) - Example 2(b) is identical to 2(a) except that different stretching conditions were used, inter alia, to form pores. The data for Example 2(b) are shown in Table 1 below. ~4. This is the same modified homo-PP used in Examples 2(a), 4, and 6-13.

[0066] Example 3 - Example 3 is identical to Example 1, except that 10% maleic anhydride modified Co-PP was added instead of the 5% maleic anhydride modified HDPE. Also, different stretching conditions were used. The data for Example 3 are shown in Tables 1 and 2 below. An SEM of Example 3 is also shown below.

[0067] Example 4 - Example 4 is the same as Example 1 except that 15% maleic anhydride modified homo-PP was added instead of the 5% maleic anhydride modified HDPE. The data for Example 4 is shown in Tables 2 and 4 below. An SEM of Example 4 is also shown below. This is the same modified homo-PP used in Examples 2(a) and (b), and 6-13.

[0068] Example 5 - Example 5 is similar to Example 1, except that 5% styrene-ethylene-propylene-styrene copolymer was used instead of the 5% maleic anhydride modified HDPE. The data for Example 5 is shown in Table 3 below.

[0069] Example 6 - Example 6 is similar to Example 1, except that 10% maleic anhydride modified homo-PP and 5% styrene-ethylene-propylene-styrene (SEPS) copolymer were added in place of the 5% maleic anhydride modified HDPE. The data for Example 6 are shown in Table 3 below. This is the same modified homo-PP used in Examples 2(a), 2(b), 4 and 7-13.

[0070] Example 7 - Example 7 is similar to Example 1 except that 10% maleic anhydride modified homo-PP plus 5% propylene-ethylene elastomer is used instead of the 5% maleic anhydride modified HDPE. The data for Example 7 is shown in Table 3 below. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, and 8-13.

[0071] Example 8 - Example 8 is similar to Example 1, except that 20% maleic anhydride modified homo-PP was used instead of the 5% maleic anhydride modified HDPE. The data for Example 8 is found in Table 4 below. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, 7, and 9-13.

[0072] Example 9 - Example 9 is similar to Example 1, except that 25% maleic anhydride modified homo-PP was used instead of the 5% maleic anhydride modified HDPE. The data for Example 9 is found in Table 4 below. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, 7, 8, and 10-13.

[0073] Examples 10-9 are similar to Example 1, except that 30% maleic anhydride modified homo-PP was used instead of the 5% maleic anhydride modified HDPE. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, 7, 8, 9, and 11-13.

[0074] Examples 11-9 are similar to Example 1, except that 35% maleic anhydride modified homo-PP was used instead of the 5% maleic anhydride modified HDPE. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, 7, 8, 9, 10, and 12-13.

[0075] Example 12 - Example 9 uses 40% maleic anhydride instead of 5% maleic anhydride modified HDPE. This example is similar to Example 1, except that an acetylated homo-PP was used. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, 6, 7, 8, 9, 10, 11, and 13.

[0076] Example 13 - Example 13 is similar to Example 1, except that 10% maleic anhydride modified homo-PP and 5% styrene-ethylene-butylene-styrene (SEBS) copolymer were added in place of the 5% maleic anhydride modified HDPE. This is the same modified homo-PP used in Examples 2(a), 2(b), 4, and 6-12.

[0077] Examples 14-26 Examples 14-26 were made by laminating two monolayer films of PP+additive with one monolayer film of PE to form a PP / PE / PP trilayer structure.

[0078] Examples 27-29 - Examples 27-29 were made by co-extruding PP+additive as described above to form a co-extruded tri-layer. PE was also co-extruded to form a co-extruded tri-layer. The two PP+additive co-extruded tri-layers were then laminated with one PE co-extruded tri-layer to form a structure such as the following (PP / PP / PP) / (PE / PE / PE) / (PP / PP / PP). Additives may be included in one or all of the layers of the PP+additive co-extruded tri-layer.

[0079] Example 30 - Example 30 was prepared similarly to Example 1, except that 5% ionomer was added instead of the 5% maleic anhydride modified high density polyethylene.

[0080] Comparative Example 1(a) - Comparative Example 1(a) is similar to Example 1 except that no additive was added. Also, different stretching conditions were used. The data for Comparative Example 1(a) can be seen in Tables 1-3 below. An SEM of Comparative Example 1(a) can also be seen below.

[0081] Comparative Example 1(b) - Comparative Example 1(b) is similar to Example 1 except that no additive was added. Also, different stretching conditions were used. The data for Comparative Example 1(b) can be seen in Tables 1 and 3 below.

[0082] Comparative Example 1(c) - Comparative Example 1(c) is similar to Example 1 except that no additive was added. The data for Comparative Example 1(c) can be found in Table 3 below.

[0083] Comparative Example 1(d) - Comparative Example 1(d) is similar to Example 1 except that no additive was added. Also, different stretching conditions were used. The data for Comparative Example 1(d) can be seen in Tables 1-3 below. An SEM of Comparative Example 1(a) can also be seen below.

[0084] result See the results in Tables 1 to 5 (Figures 1 to 5, respectively).

[0085] See SEM images at 5,000x magnification in Figures 6 to 8.

[0086] See SEM images at 20,000x magnification in Figures 9-11.

[0087] Pin Removal Force The pin removal force was measured for Example 8 and Comparative Example 2. A brief summary of the results Some advantages of maleic anhydride (MAH) functional resins include: Especially, polyaramid coating, polymer coated separator (PCS) coating, and thin ceramic coating (nano dispersion less than 1 micron) without any treatment such as corona treatment. ) ability to be covered with MAH may function as a free radical scavenger, which is important for 5V USABC applications. Electrode adhesion is enhanced; Reduce static electricity, Wettability, including improvements in wetting rate and contact angle; Improved electrode adhesion for it, Other characteristics was found to include. The SEM images at 20,000x show that even microporous membranes with 15% additive can be formed using the Celgard® dry process. It is expected that amounts up to 20%, 25%, 30% or more could be Celgard dry processed or form microporous membranes like those seen in the SEM images.

[0088] Examples 5 and 6 contain SEPS elastomer and show comparable or better puncture than the examples without SEPS elastomer.

[0089] Example 7, which contains PP elastomer, shows reduced puncture and low Gurley.

[0090] According to at least selected embodiments, aspects or objects, the present disclosure or invention may address prior problems, needs or issues and / or provide a new or improved microporous monolayer, bilayer, trilayer or multilayer membrane, separator membrane, separator, or coated separator. The membrane is preferably made from at least one resin or polymer and at least one additive. The additive may include at least one material that improves adhesion of the microporous membrane to a coating, preferably a polyaramid-containing coating, or to a different material, such as a metal surface. The improved adhesion is based on a comparison to a similar microporous membrane that does not include the at least one additive. In some preferred embodiments, the at least one additive may include, consist of, or consist essentially of a functional polymer or a combination of a functional polymer and an elastomer. In some embodiments, the functional group of the functional polymer may be maleic anhydride (MAH). Battery separators or coated separators including the new or improved microporous membranes are also disclosed. The battery separator may include a microporous membrane coated with a polyaramid-containing coating.New or improved separators, composites, batteries, lithium ion secondary batteries, and / or vehicles or devices including the separators, composites, or batteries are also disclosed.

[0091] Contact angle test: ASTM D5725: Standard Test Method for Surface Wettability and Absorbency of Sheet Materials Using an Automated Contact Angle Tester

[0092] This test method measures the contact angle of a test liquid in contact with a flat test specimen of a thin film under specified test conditions. An automated device is used to observe and measure the contact angle of a liquid drop on the top of the flat test specimen.

[0093] 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. Many changes and modifications will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

[0094] The present invention may be embodied without departing from its spirit and essential characteristics, and therefore, reference should be made to the appended claims, rather than the above specification, as indicating the scope of the invention. Components that may be used to implement the disclosed methods and systems are disclosed. These and other components are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these components are specifically contemplated and described herein for all methods and systems when disclosed, even though each of their various individual and collective combinations and permutations may not be expressly disclosed. This applies to all aspects of this 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.

[0095] The above detailed description of the structures and methods are presented for illustrative purposes only. The examples are used to disclose exemplary embodiments, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any device or system, and practicing any incorporated methods. These examples are not intended to be exhaustive or to limit the invention to the exact steps and / or forms 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 films or precursors, but may also be described including other films or precursors, such as dry process coextrusion, wet process, wet process coextrusion, BNBOPP cast film, BNBOPP cast film coextrusion, in-line slotted bed coextrusion, laminated versions, coated products, embossed or calendared versions, and / or the like. 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 include equivalent structural elements that are not substantially different from the literal language of the claims.

[0096] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein. In addition to those shown and described herein, various modifications of the compositions and methods are intended to be within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps disclosed herein are specifically described, 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 ingredients may be explicitly referred to herein or below, other combinations of steps, elements, components, or ingredients are encompassed even if not explicitly described.

[0097] 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 "about" or "approximately" from 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 is understood that the particular value forms another embodiment. It is further understood that each of the endpoints of a range is significant both in relation to the other endpoint, and independently of the other endpoint. "Optional" or "optionally" refers to the event or events described thereafter or to the extent that the event or events described thereafter are within the scope of the present invention. It is meant that a circumstance may or may not occur, and that a description includes instances where the event or circumstance occurs and instances where it does not occur.

[0098] Throughout the detailed description and claims of this specification, the word "comprise" and variations of the 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" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention and 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 descriptive or illustrative sense, rather than in a restrictive sense.

[0099] Except as noted, all numbers expressing geometric shapes, dimensions, and the like used in the specification and claims should at least be understood and 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 scope of the claims.

[0100] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. All publications cited herein and the materials cited therein are specifically incorporated by reference.

[0101] In addition, the invention illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

Claims

1. A microporous membrane made from at least one polymer or resin and at least one additive, comprising: at least one surface or layer of said microporous membrane exhibits enhanced adhesion or bond strength when compared to the adhesion or bond strength between a coating comprising polyaramid, a PCS coating, and / or a metal surface, such as an electrode, and a microporous membrane made only of said at least one polymer but not containing said at least one additive, said additive being present in any coating comprising polyaramid or metal surface in an amount of 1-50 wt % based on the total weight of said membrane; A microporous membrane that exhibits high adhesion without the need for pre-coating or pre-treating the microporous membrane to increase adhesion.

2. 10. The microporous membrane of claim 1 having on at least one surface thereof a coating comprising polyaramid, wherein the adhesion strength between the coating comprising polyaramid (or poly-aramid or aramid) is high when compared to the adhesion strength between the coating comprising polyaramid and a microporous membrane made from the at least one polymer but not containing the at least one additive.

3. 10. The microporous membrane of claim 1, wherein the at least one polymer or resin is selected from polypropylene, another polymer or resin that is immiscible or incompatible with polyaramid, and combinations thereof.

4. 4. The microporous membrane of claim 3, wherein the at least one polymer is polypropylene or a combination of polypropylene and another polymer or resin.

5. 5. The microporous membrane of claim 4, wherein the polypropylene comprises at least one of a homopolymer polypropylene, a copolymer polypropylene, a terpolymer polypropylene, and combinations thereof.

6. 10. The microporous membrane of claim 1, wherein the additive comprises a functional polymer or a functional polymer and an elastomer such as SEPS or SEBS.

7. 7. The microporous membrane of claim 6, wherein the additive comprises at least one selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, and combinations thereof.

8. The microporous membrane of any one of claims 1 to 7, wherein the additive is present in an amount of 1 to 25 wt %, based on the total weight of the membrane.

9. The microporous membrane of any one of claims 1 to 7, wherein the additive is present in an amount of 1 to 15 wt %, based on the total weight of the membrane.

10. The microporous membrane of claim 1, wherein the additive is present in an amount of 1 to 10 wt %, based on the total weight of the membrane.

11. The microporous membrane of claim 1 , wherein the membrane is a single layer membrane.

12. The microporous membrane of claim 1 , wherein the membrane is a bilayer membrane.

13. 13. The microporous membrane of claim 12, wherein at least one layer of said bilayer membrane comprises said additive.

14. 14. The microporous membrane of claim 13, wherein both layers of the bilayer membrane contain the additive.

15. 14. The microporous membrane of claim 13, wherein at least one layer of the bilayer comprises the additive in an amount of up to 50% by weight based on the weight of the layer, up to 40% by weight based on the weight of the layer, up to 30% by weight based on the weight of the layer, up to 25% by weight based on the weight of the layer, up to 20% by weight based on the weight of the layer, up to 15% by weight based on the weight of the layer, up to 10% by weight based on the weight of the layer, or up to 5% by weight based on the weight of the layer.

16. The microporous membrane of claim 1 , wherein the membrane is a multi-layer membrane.

17. 17. The microporous membrane of claim 16, wherein at least one layer of said multi-layer membrane comprises said additive.

18. 20. The microporous membrane of claim 17, wherein at least one outermost layer of said multi-layer membrane comprises said additive.

19. 20. The microporous membrane of claim 17, wherein at least one layer of the multilayer film comprises the additive in an amount of up to 50 wt.% based on the weight of the layer, up to 40 wt.% based on the weight of the layer, up to 30 wt.% based on the weight of the layer, up to 25 wt.% based on the weight of the layer, up to 20 wt.% based on the weight of the layer, up to 15 wt.% based on the weight of the layer, up to 10 wt.% based on the weight of the layer, or up to 5 wt.% based on the weight of the layer.

20. 20. The microporous membrane of claim 18, wherein at least one outermost layer of the multilayer film comprises the additive in an amount of up to 20 wt.% based on the weight of the layer, up to 15 wt.% based on the weight of the layer, up to 10 wt.% based on the weight of the layer, or up to 5 wt.% based on the weight of the layer.

21. 10. The microporous membrane of claim 1, wherein at least one surface of said microporous membrane exhibits reduced pin removal force, more controlled pore size, improved electrolyte wetting, improved ion trapping, enhanced toughness and combinations thereof when compared to a microporous membrane made from said at least one polymer but not containing any additives.

22. 22. The microporous membrane of claim 21, wherein at least one surface of the microporous membrane exhibits reduced pin removal force when compared to a microporous membrane made from the at least one polymer but not containing any additives.

23. 23. The microporous membrane of claim 22, wherein the at least one surface exhibiting reduced pin removal force is not the same as the at least one surface exhibiting improved adhesion.

24. 23. The microporous membrane of claim 22, wherein the at least one additive comprises at least one lubricant.

25. 25. The microporous membrane of claim 24, wherein the lubricant is amphiphilic.

26. 25. The microporous membrane of claim 24, wherein the lubricant is a fatty acid salt.

27. The fatty salts include lithium stearate, sodium stearate and potassium stearate.

27. The microporous membrane of claim 26, wherein the polymer is selected from the group consisting of tungsten, tungsten, tungsten oxide, tungsten fluoride ...

28. 25. The microporous membrane of claim 24, wherein the lubricant is a siloxane or polysiloxane containing compound that contains one or more siloxy functional groups.

29. 30. The microporous membrane of claim 28, wherein the lubricant is an ultra-high molecular weight polysiloxane.

30. 22. The microporous membrane of claim 21, wherein at least one surface of the microporous membrane exhibits more controlled pore size when compared to a microporous membrane made from the at least one polymer but not containing any additives.

31. 31. The microporous membrane of claim 30, wherein the at least one additive comprises a homopolymer, copolymer, or terpolymer having a different molecular weight than the polymer or resin from which the microporous membrane is made.

32. 22. The microporous membrane of claim 21, wherein at least one surface of the microporous membrane exhibits improved wetting with an electrolyte when compared to a microporous membrane made from the at least one polymer but not containing any additives.

33. 22. The microporous membrane of claim 21, wherein at least one surface of the microporous membrane exhibits improved ion capture when compared to a microporous membrane made from the at least one polymer but not containing any additives.

34. 22. The microporous membrane of claim 21, wherein at least one surface of the microporous membrane exhibits enhanced toughness when compared to a microporous membrane made from the at least one polymer but not containing any additives.

35. 35. The microporous membrane of claim 34, wherein the at least one additive comprises an ionomer resin.

36. 10. The microporous membrane of claim 1, wherein the membrane is coated with a coating comprising polyaramid on at least one surface that exhibits high adhesive strength with the coating comprising polyaramid.

37. 37. The microporous membrane of claim 36, wherein the coating comprises a polyaramid and at least one of an inorganic filler, an organic filler, or a combination thereof.

38. 10. The microporous membrane of claim 1, wherein the at least one surface exhibiting adhesive strength with a metal surface is in direct contact with the metal surface.

39. 10. The microporous membrane of claim 1, wherein said at least one surface is coated or treated to enhance adhesive strength even further, for example by corona treatment or by providing a PE latex coating.

40. A battery separator comprising the microporous membrane of any one of claims 1 to 39.

41. A lithium ion secondary battery comprising the separator of claim 40.

42. 41. A composite comprising the battery separator of claim 40 in direct contact with an electrode for a lithium ion secondary battery.

43. A vehicle or device comprising the battery separator, battery or composite of claims 40-42.

44. A microporous membrane made from at least one polymer or resin and at least one additive, said additive being a functional polymer selected from acid copolymers, ionomers, and maleic anhydride modified PP or PE homopolymer and / or copolymer resins, said additive comprising: enhance adhesion between a coating layer, including a polyaramid-containing coating, a ceramic coating, a polymeric coating, or the like, and at least one surface of the microporous membrane; enhance adhesion between a metal surface, such as an electrode, and at least one surface of the microporous membrane; reducing pin removal on at least one surface of the microporous membrane; enhance wettability of the microporous membrane with an electrolyte on at least one surface of the membrane; Enhance ion capture on at least one surface of the microporous membrane; enhance the toughness or durability of at least one surface of the microporous membrane; Controlling the pore size of at least one surface of the microporous membrane; reducing static electricity on at least one surface of the microporous membrane; Increase puncture strength, and / or enhances ion transport across the membrane; A microporous membrane that performs at least one of the following functions:

45. 45. The microporous membrane of claim 44, wherein the at least one additive enhances adhesion between a coating layer and at least one surface of the microporous membrane.

46. 46. ​​The microporous membrane of claim 45, wherein the coating layer comprises a polyaramid.

47. 45. The microporous membrane of claim 44, wherein the functional polymer is at least one selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, and combinations thereof.

48. 45. The microporous membrane of claim 44, wherein the at least one additive enhances adhesion between a metal surface and at least one surface of the microporous membrane.

49. 49. The microporous membrane of claim 48, wherein the metal surface is made from an electrode material, for example an electrode material for a lithium ion battery.

50. 49. The microporous membrane of claim 48, wherein the additive is a functional polymer or a combination of a functional polymer and an elastomer.

51. 51. The microporous membrane of claim 50, wherein the functional polymer is at least one selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, and combinations thereof.

52. 45. The microporous membrane of claim 44, wherein the at least one additive reduces pin removal of at least one surface of the microporous membrane.

53. 53. The microporous membrane of claim 52, wherein the microporous membrane comprises the at least one additive comprising a lubricant.

54. 54. The microporous membrane of claim 53, wherein the lubricant is amphiphilic.

55. 54. The microporous membrane of claim 53, wherein the lubricant is a fatty acid salt.

56. 56. The microporous membrane of claim 55, wherein the fatty salt is selected from lithium stearate, sodium stearate, and potassium stearate.

57. 54. The microporous membrane of claim 53, wherein the lubricant is a siloxane or polysiloxane containing compound that contains one or more siloxy functional groups.

58. 54. The microporous membrane of claim 53, wherein the lubricant is an ultra-high molecular weight polysiloxane.

59. 45. The microporous membrane of claim 44, wherein the at least one additive enhances wettability with an electrolyte on at least one surface of the microporous membrane.

60. 45. The microporous membrane of claim 44, wherein the at least one additive reduces pin removal of at least one surface of the microporous membrane.

61. 45. The microporous membrane of claim 44, wherein the at least one additive enhances ion capture on at least one surface of the microporous membrane.

62. 45. The microporous membrane of claim 44, wherein the at least one additive enhances toughness or durability of at least one surface of the microporous membrane.

63. 45. The microporous membrane of claim 44, wherein the at least one additive controls the pore size of at least one surface of the microporous membrane.

64. 64. The microporous membrane of claim 63, wherein the at least one additive comprises a homopolymer, copolymer, or terpolymer having a different molecular weight than the polymer or resin from which the microporous membrane is made.

65. 45. The microporous membrane of claim 44, wherein the at least one additive reduces static electricity on at least one surface of the microporous membrane.

66. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least two of said functions.

67. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least three of said functions.

68. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least four of said functions.

69. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least five of said functions.

70. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least six of said functions.

71. 5. The at least one additive performs at least seven of said functions.

5. The microporous membrane according to claim 4.

72. 45. The microporous membrane of claim 44, wherein the at least one additive fulfills at least eight, at least nine, or all ten of the functions.

73. 45. The microporous membrane of claim 44, wherein the microporous membrane is a single layer, bilayer or multilayer microporous membrane.

74. 74. The microporous membrane of claim 73, wherein the microporous membrane is a monolayer membrane and the resin or polymer produced is a polyolefin resin comprising a polyethylene homopolymer, copolymer or terpolymer, a polypropylene homopolymer, copolymer or terpolymer or a mixture thereof.

75. 74. The microporous membrane of claim 73, wherein the microporous membrane is a bilayer membrane and the resin or polymer produced is a polyolefin resin comprising a polyethylene homopolymer, copolymer or terpolymer, a polypropylene homopolymer, copolymer or terpolymer or a mixture thereof.

76. 74. The microporous membrane of claim 73, wherein the microporous membrane is a multilayer membrane and the resin or polymer produced is a polyolefin resin comprising a polyethylene homopolymer, copolymer or terpolymer, a polypropylene homopolymer, copolymer or terpolymer, or a mixture thereof.

77. 77. The microporous membrane of claim 76, wherein the at least one additive is present in at least one outermost layer of the multi-layer membrane.

78. 45. The microporous membrane of claim 44, wherein the at least one additive enhances adhesion between a coating layer and at least one surface of the microporous membrane and reduces pin removal on a different surface of the microporous membrane with the same or a different additive.

79. 45. The microporous membrane of claim 44, wherein the at least one additive performs at least one of the functions on at least one surface of the microporous membrane, and the same or a different additive performs at least one different function on a different surface of the microporous membrane.

80. A battery separator comprising the microporous membrane of any one of claims 44 to 79.

81. 81. A lithium ion secondary battery comprising the separator of claim 80.

82. 81. A composite comprising the battery separator of claim 80 in direct contact with an electrode for a lithium ion secondary battery.

83. A vehicle or device comprising the battery separator, battery or composite of claims 80-82.

84. 1. A multi-layer microporous membrane comprising an outermost layer of the membrane, wherein one outermost layer of the membrane comprises at least one additive, the additive comprising: enhancing adhesion between a coating layer and at least one surface of the microporous membrane, the coating layer comprising at least one of a polyaramid-containing coating layer, a ceramic coating layer, and a polymer-containing coating layer; enhance adhesion between a metal surface, including an electrode, and at least one surface of the microporous membrane; reducing pin removal on at least one surface of the microporous membrane; enhance wettability of the microporous membrane with an electrolyte on at least one surface of the membrane; Enhance ion capture on at least one surface of the microporous membrane; enhance the toughness or durability of at least one surface of the microporous membrane; Controlling the pore size of at least one surface of the microporous membrane; reducing static electricity on at least one surface of the microporous membrane; Increase puncture strength, and enhances ion transport across the membrane; A multi-layer microporous membrane that performs at least one of the following functions:

85. 85. The multi-layer microporous membrane of claim 84, wherein both outermost layers of the membrane comprise at least one additive.

86. 86. The multi-layer microporous membrane of claim 85, wherein the outermost layers of the membrane comprise different additives.

87. 86. The multi-layer microporous membrane of claim 85, wherein the outermost layers of the membrane comprise the same additive.

88. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 0.1 to 5 microns.

89. 85. The multi-layer, microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 0.1 to 3 microns.

90. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 0.1 to 2.5 microns.

91. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 0.1 to 2 microns.

92. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 1 to 20 microns.

93. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 1 to 15 microns.

94. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 2 to 10 microns.

95. 85. The multi-layer microporous membrane of claim 84, wherein one or both of the outermost layers have a thickness of 3 to 5 microns.

96. 85. The microporous membrane of claim 84, wherein the at least one additive enhances adhesion between a coating layer and at least one surface of the microporous membrane.

97. 97. The microporous membrane of claim 96, wherein the coating layer comprises a polyaramid.

98. 97. The microporous membrane of claim 96, wherein the additive is a functional polymer or a combination of a functional polymer and an elastomer that contains olefinic groups, polar groups, or both.

99. The functional polymer is a maleic anhydride modified polyethylene, a maleic anhydride modified polypropylene, 99. The microporous membrane of claim 98, wherein the at least one selected from the group consisting of propylene and combinations thereof.

100. 85. The microporous membrane of claim 84, wherein the at least one additive enhances adhesion between a metal surface and at least one surface of the microporous membrane.

101. 101. The microporous membrane of claim 100, wherein the metal surface is made from an electrode material, for example an electrode material for a lithium ion battery.

102. 101. The microporous membrane of claim 100, wherein the additive is a functional polymer that contains polar groups, olefinic groups, or both.

103. 103. The microporous membrane of claim 102, wherein the functional polymer is at least one selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, and combinations thereof.

104. 85. The microporous membrane of claim 84, wherein the at least one additive reduces pin removal of at least one surface of the microporous membrane.

105. 105. The microporous membrane of claim 104, wherein the at least one additive comprises a lubricant.

106. 106. The microporous membrane of claim 105, wherein the lubricant is amphiphilic.

107. 106. The microporous membrane of claim 105, wherein the lubricant is a fatty acid salt.

108. 108. The microporous membrane of claim 107, wherein the fatty salt is selected from lithium stearate, sodium stearate, and potassium stearate.

109. 106. The microporous membrane of claim 105, wherein the lubricant is a siloxane or polysiloxane containing compound that contains one or more siloxy functional groups.

110. 106. The microporous membrane of claim 105, wherein the lubricant is an ultra-high molecular weight polysiloxane.

111. 85. The microporous membrane of claim 84, wherein the at least one additive enhances wettability with an electrolyte on at least one surface of the microporous membrane.

112. 85. The microporous membrane of claim 84, wherein the at least one additive reduces pin removal of at least one surface of the microporous membrane.

113. 85. The microporous membrane of claim 84, wherein the at least one additive enhances ion capture on at least one surface of the microporous membrane.

114. 85. The microporous membrane of claim 84, wherein the at least one additive enhances toughness of at least one surface of the microporous membrane.

115. 115. The microporous membrane of claim 114, wherein the at least one additive comprises an ionomer resin.

116. 85. The microporous membrane of claim 84, wherein the at least one additive controls the pore size of at least one surface of the microporous membrane.

117. 117. The microporous membrane of claim 116, wherein the at least one additive comprises a homopolymer, copolymer, or terpolymer having a different molecular weight than the polymer or resin from which the microporous membrane is made.

118. 85. The microporous membrane of claim 84, wherein the at least one additive reduces static electricity on at least one surface of the microporous membrane.

119. 85. The microporous membrane of claim 84, wherein said at least one additive performs at least two of said functions.

120. 85. The microporous membrane of claim 84, wherein said at least one additive performs at least three of said functions.

121. 85. The microporous membrane of claim 84, wherein said at least one additive performs at least four of said functions.

122. 45. The microporous membrane of claim 44, wherein said at least one additive performs at least five of said functions.

123. 85. The microporous membrane of claim 84, wherein said at least one additive performs at least six of said functions.

124. 85. The microporous membrane of claim 84, wherein said at least one additive performs at least seven of said functions.

125. 85. The microporous membrane of claim 84, wherein the at least one additive fulfills at least eight, at least nine, or all ten of the functions.

126. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 60 microns.

127. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 50 microns.

128. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 40 microns.

129. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 30 microns.

130. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 20 microns.

131. 85. The microporous membrane of claim 84, wherein the total thickness of the membrane is between 1 micron and 15 microns.

132. A battery separator comprising the microporous membrane of any one of claims 84 to 131.

133. A lithium ion secondary battery comprising the separator of claim 132.

134. 133. A composite comprising the battery separator of claim 132 in direct contact with an electrode for a lithium ion secondary battery.

135. A vehicle or device comprising the battery separator, battery or composite of claims 132-134.

136. 10. The microporous membrane of claim 1, wherein the additive is at least one of an acid copolymer, an ionomer, and a maleic anhydride modified PP or PE homopolymer and / or copolymer resin.

137. 45. The microporous membrane of claim 44, wherein the additive is at least one of an acid copolymer, an ionomer, and a maleic anhydride modified PP or PE homopolymer and / or copolymer resin.

138. 85. The microporous membrane of claim 84, wherein the additive is at least one of an acid copolymer, an ionomer, and a maleic anhydride modified PP or PE homopolymer and / or copolymer resin.

139. A textile article comprising the microporous membrane of claim 44.

140. A textile article comprising the microporous membrane of claim 84.

141. 45. A laminated textile article comprising at least one microporous membrane according to claim 44.

142. 142. The laminated fibrous product of claim 141, comprising two or more microporous membranes of claim 44.

143. 142. The laminated fibrous product of claim 141, comprising three or more microporous membranes of claim 44.

144. 142. The laminated fibrous product of claim 141, further comprising at least one woven, nonwoven, porous or microporous layer.

145. 85. A laminated textile article comprising at least one microporous membrane according to claim 84.

146. 146. The layered fibrous product of claim 145, comprising two or more microporous membranes of claim 84.

147. 146. The laminated fibrous product of claim 145, comprising three or more microporous membranes of claim 44.

148. The laminated fibrous product of claim 145, further comprising at least one woven, nonwoven, porous or microporous layer.

149. 140. Apparel or outdoor gear comprising the textile product of claim 139.

150. Clothing or outdoor gear comprising the textile product of claim 140.

151. 142. Apparel or outdoor gear comprising the laminated textile product of claim 141.

152. 146. Apparel or outdoor gear comprising the laminated textile product of claim 145.

153. A textile product comprising the microporous membrane of claim 1.

154. A microporous membrane made from at least one polymer or resin and at least one additive, comprising: At least one surface or layer of the microporous membrane exhibits increased adhesion or bond strength when compared to the adhesion or bond strength between a coating comprising polyaramid, a PCS coating, and / or a metallic surface, such as an electrode, and a microporous membrane made only of the at least one polymer but not containing the at least one additive, and exhibits increased adhesion without pre-coating or pre-treating the microporous membrane to increase adhesion. Laminated textile products or clothing or outdoor equipment including:

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