Polyamide-imide coated separator for high-energy rechargeable lithium batteries

Abstract

An improved separator for high energy or high voltage rechargeable lithium batteries is provided. The present invention is preferably directed to a polyamide-imide coated membrane, separator film, or separator for lithium batteries and corresponding batteries. The separator preferably includes a porous or microporous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high-temperature performance (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc.

Description

[Technical Field]

[0001] This disclosure or invention is preferably directed to polyamide-imide-coated membranes, separator membranes, or separators for lithium batteries, e.g., high-energy or high-voltage rechargeable lithium batteries, and corresponding batteries. The separator preferably includes a porous or microporous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high-temperature performance (HTMI function), prevent electronic shorting at temperatures above 200°C, etc. The microporous polymer base layer may be adapted at least to retain a liquid, gel, or polymer electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown function). The polyamide-imide coated separator may be adapted, for example, to keep electrodes apart at high temperatures, impart oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high temperature capability (HTMI function), prevent electronic shorting at temperatures above 200°C, increase pin puncture strength, and / or inhibit ion flow between the anode and cathode in the event of thermal runaway (shutdown function). Although secondary lithium battery uses may be preferred, the polyamide-imide coated membrane may be used in batteries, cells, primary batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or as a layer or component in other applications, devices, etc.

[0002] In at least selected embodiments, objects, or aspects, this disclosure or invention is directed to a polyamide-imide-coated membrane, separator film, or separator for secondary lithium batteries, such as high-energy or high-voltage rechargeable lithium-ion batteries, polymer batteries, or metal batteries, and corresponding batteries. The separator preferably includes a porous or microporous polyamide-imide coating or layer on at least one side of a polymer microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high-temperature performance (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc. The microporous polymer substrate may be adapted at least to retain a liquid, gel, or polymer electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown functionality). The polyamide-imide coated separator may be adapted, for example, to keep the electrodes apart at high temperatures, to provide oxidation resistance, to inhibit dendrite growth, to add dimensional stability, to reduce shrinkage, to add high temperature capability (HTMI function), to prevent electronic shorting at temperatures above 200°C, to increase pin puncture strength, and / or to inhibit ion flow between the anode and cathode in the event of thermal runaway (shutdown function).

[0003] In at least some embodiments, objects, or aspects, this disclosure or invention is directed to a polyamide-imide battery separator. The polyamide-imide battery separator may comprise, consist of, or consist essentially of a non-porous, semi-porous, microporous, mesoporous, macroporous, or nanoporous polyamide-imide layer or film. In some preferred embodiments, the polyamide-imide battery separator may comprise, consist of, or consist essentially of a polyamide-imide layer or film that is both porous and ionically conductive. For example, the layer or film may conduct lithium ions. In other preferred embodiments, the polyamide-imide battery separator may comprise, consist of, or consist essentially of a polyamide-imide layer or film that is non-porous or only semi-porous but also ionically conductive. For example, the layer or film may conduct lithium ions.

[0004] Separators for high-energy or high-voltage rechargeable lithium batteries and high-energy or high-voltage rechargeable lithium batteries are disclosed herein. According to at least certain embodiments, objectives, or aspects, this disclosure or invention is directed to polyimide-coated separators for high-energy or high-voltage rechargeable lithium batteries and corresponding batteries. The separator preferably includes a porous, non-porous, or semi-porous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high-temperature performance (HTMI functionality), prevent electronic shorts at temperatures above 200°C, etc. The microporous polymer layer may be adapted to at least retain liquid electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown function).

[0005] The polyamide-imide of the polyamide-imide coating or layer may be selected from the group consisting of pure polyamide-imide, 30% glass fiber polyamide-imide, 30% carbon fiber polyamide-imide, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations of the above.

[0006] In some embodiments, the battery separator consists of or consists essentially of a polyamide-imide layer or film. The polyamide-imide layer or film in such embodiments is not a coating on a microporous polymeric substrate. The polyamide-imide layer is free-standing. [Background technology]

[0007] High-energy rechargeable lithium batteries may have anodes with an energy capacity of at least 372 milliamp-hours per gram (mAh / g). Such anodes may include, for example, lithium metal, lithium alloys (e.g., lithium aluminum), and mixtures of lithium metal or lithium alloys with materials such as carbon, nickel, and copper.

[0008] High voltage rechargeable lithium batteries may have a voltage of at least 4.5 V, and even greater than 4.7 V. Such batteries may have an anode with a lithium intercalation or insertion compound.

[0009] The commercial success of certain high energy and high voltage secondary or rechargeable lithium ion batteries has been hampered by sustained cycling or safety issues or challenges.

[0010] One common solution is a ceramic coated separator (CCS), such as described in U.S. Patent No. 6,432,586, which is incorporated herein by reference in its entirety. Difficulties associated with the use of certain CCS in selected batteries or cells include the fact that ceramic particles can flake off during cell manufacturing, that ceramic coatings are abrasive and difficult to slit, and can wear down equipment and slitter blades, and that ceramic coatings add thickness, cost, and complexity.

[0011] Some proposals have been made to use gel or polymer electrolytes instead of CCS. These gel or polymer electrolytes may not have sufficient dimensional stability (they do not hold their shape) and may not have good ionic conductivity. Liquid electrolytes may have 10x the conductivity of gel or polymer electrolytes.

[0012] Additionally, gel or polymer electrolytes may not prevent dendrite shorting. Lithium dendrite growth can occur after repeated charge-discharge cycles. While dendrite growth is a potential issue with any lithium battery, the severity of the issue increases with the use of high-energy anodes (e.g., metal, metal alloy, or pure carbon intercalation anodes). When lithium dendrites grow and penetrate the separator, an internal short circuit of the battery occurs (any direct contact between the anode and cathode is referred to as an "electronic" short circuit, and contacts made by dendrites are a type of electronic short circuit). Some short circuits (i.e., soft short circuits) caused by very small dendrites may only reduce the cycling efficiency of the battery. Other short circuits, such as hard short circuits, can result in thermal runaway of the lithium battery, which is a serious safety issue for lithium rechargeable batteries. Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, there is a need for improved separators for at least high energy or high voltage rechargeable lithium batteries. [Means for solving the problem]

[0014] In accordance with at least selected embodiments of the present invention or disclosure, new or improved inventive separators may address the above-mentioned needs, problems, or challenges and / or may provide polyamide-imide coated membranes, separators, or separator membranes adapted for use as layers or components in batteries, cells, primary batteries, secondary batteries, high energy or high voltage rechargeable lithium batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or other applications, devices, etc. In accordance with at least some selected embodiments of the present invention or disclosure, new or improved inventive separators may address the above-mentioned needs, problems, or challenges and / or may provide polyamide-imide coated membranes, films, layers, separators, or separator membranes adapted for use as layers or components in batteries, cells, primary batteries, secondary batteries, high energy or high voltage rechargeable lithium batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or other applications, devices, etc.

[0015] This disclosure or invention is preferably directed to polyamide-imide coated membranes, separator films, or separators for lithium batteries, e.g., high-energy or high-voltage rechargeable lithium batteries, and corresponding batteries. The separator preferably comprises a porous or microporous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may comprise other polymers, additives, fillers, etc. Polyamide-imide coating The polyamide-imide coated separator may be adapted, for example, to provide oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high temperature capability (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc. The microporous polymer substrate may be adapted at least to retain a liquid, gel, or polymer electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown functionality). The polyamide-imide coated separator may be adapted, for example, to keep the electrodes apart at high temperatures, provide oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high temperature capability (HTMI functionality), prevent electronic shorting at temperatures above 200°C, increase puncture strength, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown functionality). Although secondary lithium battery uses may be preferred, the polyamide-imide coated membranes may be used in batteries, cells, primary batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or as layers or components in other applications, devices, etc.

[0016] In at least selected embodiments, objects, or aspects, this disclosure or invention is directed to a polyamide-imide-coated membrane, separator film, or separator for secondary lithium batteries, such as high-energy or high-voltage rechargeable lithium-ion batteries, polymer batteries, or metal batteries, and corresponding batteries. The separator preferably includes a porous or microporous polyamide-imide coating or layer on at least one side of a polymer microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high-temperature performance (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc. The microporous polymer substrate may be adapted at least to retain a liquid, gel, or polymer electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown functionality). The polyamide-imide coated separator may be adapted, for example, to keep the electrodes apart at high temperatures, to provide oxidation resistance, to inhibit dendrite growth, to add dimensional stability, to reduce shrinkage, to add high temperature capability (HTMI function), to prevent electronic shorting at temperatures above 200°C, to increase pin puncture strength, and / or to inhibit ion flow between the anode and cathode in the event of thermal runaway (shutdown function).

[0017] The polyamide-imide of the polyimide coating or layer may be pure polyamide-imide, 30% glass fiber polyamide-imide, 30% carbon fiber polyamide-imide, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations thereof. As will be understood by those skilled in the art, the "pure" in "pure" polymer means that the polymer is essentially a pure compound, consisting only of molecules of the polymer from which it is produced.

[0018] Disclosed herein are separators for high-energy or high-voltage rechargeable lithium batteries, and high-energy or high-voltage rechargeable lithium batteries. According to at least certain embodiments, objectives, or aspects, this disclosure or invention is directed to polyamide-imide coated separators for high-energy or high-voltage rechargeable lithium batteries and corresponding batteries. The separator preferably comprises a porous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high temperature capability (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc. The microporous polymer layer may be adapted at least to retain liquid electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown functionality).

[0019] According to at least certain embodiments, this disclosure or invention is directed to new or improved separators for high-energy or high-voltage rechargeable lithium batteries and corresponding batteries. The separators include at least one polyamide-imide layer, treatment, material, deposition, or coating and at least one polymeric porous or microporous substrate. The polyamide-imide coated separator is adapted to at least inhibit dendrite growth and prevent electronic shorting. The polymeric substrate is adapted to at least inhibit ion flow between the anode and cathode in the event of thermal runaway.

[0020] The general chemical structure of polyamide-imide is shown below in Formula 1:

[0021] [ka]

[0022] In this formula, Ar is an aryl group, and n is an integer equal to or greater than 1. An aryl group is understood to be a functional group or substituent containing, consisting of, or consisting essentially of an aromatic ring. For example, aryl may be at least one selected from the group consisting of phenyl, tolyl, xylyl, naphthyl, phenyl ether, etc. Polyamide-imides (sometimes abbreviated as PAI) are generally prepared from isocyanates and TMA (trimellitic anhydride) in N-methyl-2-pyrrolidone (NMP). Polyamide-imides have high heat resistance. An example of a commercially available PAI is Torlon®, manufactured by Solvay Specialty Polymer. Another example is VYLOMAX®, available from Toyobo. Another example is Duratron® by Quadrant Plastics. Other companies that manufacture PAI include Innotek Technology Ltd., Axalta Coating Systems, LLC, Toyobo Co., Ltd., Nuplex Resins, LLC, FujiFilm, Hitachi Resins, LLC, Drake Plastics Ltd. Co., Mitsubishi Shoji, Solvay SA, Kermel, Elantas, Shanghai Songhan Plastics Technology Co., Ltd., and Ensinger GmbH. Polyamide-imides are amorphous polymers, either thermosetting or thermoplastic, that possess exceptional mechanical, thermal, and chemical resistance properties. PAIs combine the properties of both polyamides and polyimides, such as: , exhibiting a combination of high strength, melt processability, exceptionally high heat capacity, and broad chemical resistance.

[0023] By one or more optionally preferred processes, an HTMI polymer and an ion-conducting polymer can be mixed with a solvent to form a coating solution, which can be used to form the HTMI polymer coatings, films, or layers described herein. In another optionally preferred embodiment, an HTMI polymer, an ion-conducting polymer, and a ceramic can be mixed with a solvent to form a coating slurry, which can be used to form the HTMI-polymer coatings, films, or layers described herein. The HTMI polymer, in some embodiments, can be polyamide-imide, but is not limited to polyamide-imide. The ion-conducting polymer can be in the form of particles or beads in some embodiments. The ion-conducting polymer can be PVDF, e.g., PVDF-HFP, where the amount of HFP is between 1 and 35%. The ion-conducting polymer is not limited, however. The ceramic, in some embodiments, can be silica, alumina, or a combination thereof. The ceramic is not limited, however. Any ceramic compatible with the battery in which the separator will be used can be used. For example, alumina can be used. Additionally, when the ceramic is to be removed from the coating, a ceramic that is not compatible with the battery in which the separator will be used may be used. For example, silica may be used to remove it from a layer, film, or coating. For example, it may be removed using HF. In some embodiments, the solvent may be NMP, but is not so limited. Any solvent that can dissolve the HTMI polymer and the ion-conducting polymer may be used. For example, a solvent that can dissolve polyamide-imide and PVDF or PVDF-HFP may be used. Known solvents for polyamide-imide include dipolar aprotic solvents, such as NMP, DMAC, DMF, and DMSO, at a solids content of at least 35%.

[0024] The coating solution or slurry may be coated on a porous or microporous base film, or on any other suitable substrate, such as a glass plate. When forming a free-standing HTMI-polymer coating, film, or layer, the coating solution or slurry may be formed on a glass plate or other substrate from which the final film, coating, or layer may be removed. The porous or microporous base film may be a dry-process porous or microporous base film, including any microporous film sold under the trademark Celgard. Dry-process base films, such as polyolefin dry-process base films, may be preferred, especially those made from polypropylene, although wet-process, particle-stretched, beta-nucleated biaxially oriented polypropylene (BNBOPP), and other microporous membranes or films may also be used.

[0025] Once the coating slurry or coating solution has been coated to form a film, coating, or layer, the solvent may be removed or substantially removed. The solvent may be removed or substantially removed by heating in an oven or by immersing the film, coating, or layer in an aqueous solution and then drying the film, coating, or layer. The aqueous solution may be greater than 50% water by volume. In some preferred embodiments, the aqueous solution is 100% water or pure water. The immersion time may be from about 1 minute to about 1 hour, from about 1 minute to about 50 minutes, from about 1 minute to about 40 minutes, from about 1 minute to about 30 minutes, from about 1 minute to about 20 minutes, from about 1 minute to about 10 minutes, or from about 1 minute to about 5 minutes. About 5 minutes means 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes, or 5 minutes ± 5 minutes. Drying may be accomplished by oven drying or air drying.

[0026] In some embodiments, removal or substantial removal of the solution using an aqueous solution may also result in the removal of the polymer. For example, the HTMI polymer, the ion-conducting polymer, or both may be removed. This may result in the formation of pores or interstices in the film, layer, or coating. While not wishing to be bound by any particular theory, immersion of the films, layers, or coatings described herein in an aqueous solution or 100% water is believed to result in a phase inversion process that removes the solvent and some of the polymer from the film, layer, or coating. The extent of polymer removal is believed to depend on factors, particularly the immersion time. Longer immersion times are believed to result in more polymer removal.

[0027] In embodiments in which a coating slurry containing a ceramic is used, the ceramic may or may not be removed from the coating, film, or layer. If the ceramic is not compatible with the battery in which the separator is intended to be used, the ceramic should be removed. For example, silica may be incompatible with Li-ion batteries and should be removed when the separator is used in such batteries. For example, silica may be removed using HF. If the ceramic is compatible with the battery in which the separator is intended to be used, the ceramic does not need to be removed. For example, when the separator is intended to be used in Li-ion batteries, alumina may be used and does not need to be removed from the coating, film, or layer. While not wishing to be bound by any theory, it is believed that the addition of a ceramic can reduce the Gurley and ER of the film, coating, or layer. The amount of ceramic in the coating slurry may be 1 to 50%, 1 to 40%, 1 to 30%, 1 to 40%, 1 to 20%, 1 to 10%, or 1 to 5% on a total solids basis. The final coating, film, or layer may have different amounts of ceramic depending on whether the ceramic is removed, partially removed, or not removed.

[0028] For the purpose of illustrating the invention, there is shown in the drawings forms which are presently preferred; it is to be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. [Brief explanation of the drawings]

[0029] [Figure 1] 1 shows a schematic diagram of a one or two side coated separator of the present invention, where one or both sides of a porous substrate are coated with a polyamide-imide or HTMI coating. [Figure 2] 1 is a photograph of a wet coating, film, or layer according to some embodiments described herein. [Figure 3] 1 is a table showing certain results for Examples 1 and 2 described herein. [Figure 4] 1 is a table showing certain properties and results for the present invention and comparative embodiments described herein. [Figure 5A] 1 includes tables for SEM of certain embodiments described herein. [Figure 5B] 1 includes tables for SEM of certain embodiments described herein. [Figure 6] 1 is a photograph showing that certain embodiments herein are wetted by electrolyte. [Figure 7] 1 is a table containing certain characteristics and SEMs for embodiments described herein. [Figure 8] 1 is a cross-sectional view of the interior of an exemplary battery according to one embodiment herein. DETAILED DESCRIPTION OF THE INVENTION

[0030] A typical lithium battery (or cell) includes a lithium metal or alloy anode, a cathode, and a separator between the anode and cathode, all packaged within a can or pouch in a cylindrical or "jellyroll" cell, or a prismatic or laminated cell. The present invention is not limited to a particular battery or cell configuration and may also be well suited to button cells, polymer cells, and the like. Additionally, the electrolyte may be liquid (organic or inorganic), or gel (or polymer). While the present invention is described with respect to a cylindrical cell having a liquid organic electrolyte for convenience, it is not so limited and may find use in other cell types (e.g., energy storage systems, capacitors, composite cells, and capacitors) and configurations.

[0031] Optionally, preferred anodes should have a high energy or high voltage capability or capacity, preferably 372 mAh / g or greater, preferably 700 mAh / g or greater, and most preferably 1000 mAh / g or greater. Preferred anodes may be constructed from lithium metal foil or lithium alloy foil (e.g., lithium aluminum alloy), or mixtures of lithium metal and / or lithium alloys and materials such as carbon (e.g., coke, graphite), nickel, and copper. The anode may include a lithium-containing intercalation compound or a lithium-containing insertion compound.

[0032] The cathode may be any cathode compatible with the anode and may include an intercalation compound, an insertion compound, or an electrochemically active polymer. Suitable intercalation materials include, for example, MoS2, FeS2, MnO2, TiS2, NbSe3, LiCoO2, LiNiO2, LiMn2O4, V6O13, V2O5, and CuCl2. Suitable cathode polymers include, for example, polyacetylene, polypyrrole, polyaniline, and polythiophene.

[0033] The electrolyte may be a liquid or a gel (or polymer). Typically, the electrolyte is primarily composed of a salt and a medium (e.g., in a liquid electrolyte, the medium may be referred to as a solvent; in a gel electrolyte, the medium may be referred to as a polymer matrix). The salt may be a lithium salt. Examples of lithium salts include LiPF6, LiAsF6, and LiCF3. SO, LiN(CFSO), LiBF, and LiClO, BETTE electrolyte (commercially available from 3M Corp. of Minneapolis, Minn.), and combinations thereof. Solvents can include, for example, ethylene carbonate (EC), propylene carbonate (PC), EC / PC, 2-MeTHF (2-methyltetrahydrofuran) / EC / PC, EC / DMC (dimethyl carbonate), EC / DME (dimethylethane), EC / DEC (diethyl carbonate), EC / EMC (ethyl methyl carbonate), EC / EMC / DMC / DEC, EC / EMC / DMC / DEC / PE, PC / DME, and DME / PC. Examples of the electrolyte polymer matrix include PVDF (polyvinylidene fluoride), PVDF:THF (PVDF:tetrahydrofuran), PVDF:CTFE (PVDF:chlorotrifluoroethylene), PVDF-HFP, PAN (polyacrylonitrile), and PEO (polyethylene oxide).

[0034] 1 and 2, an exemplary separator includes at least an HTMI-polymer-containing coating or layer on at least one side of a porous layer, base film, or membrane. In some embodiments, the HTMI-polymer-containing coating or layer is a polyamide-imide coating or layer. In a battery, the HTMI-polymer-containing coating or layer or polyamide-imide coating or layer during normal battery or cell operating conditions must be sufficiently ionically conductive to allow ion flow between the anode and cathode so that electrical current can be produced by the cell in a desired amount. In some embodiments, this can be achieved by including an ion-conducting additive, such as an ion-conducting polymer, in the HTMI polymer- or polyamide-imide-containing coating or layer. In some embodiments, this can be achieved by including a ceramic in the coating and optionally removing the ceramic to create gaps, pores, or holes. The coating and base film should adhere well to each other. The coating and base film layer may be formed by lamination, coextrusion, deposition, or coating processes. The HTMI-polymer- or polyamide-imide-containing coating may be either a coating, a discrete layer, or a free-standing layer having a thickness ranging from 0.001 micron to 50 microns, preferably from 0.01 micron to 15 microns or less. The polymeric microporous layer is preferably a discrete membrane having a thickness ranging from 5 microns to 50 microns, preferably from 4 microns to 12 microns or more. The overall thickness of the separator is in the range of 5 microns to 100 microns, preferably from 6 microns to 25 microns.

[0035] The HTMI or polyamide-imide coating may be porous, microporous, semi-porous, or non-porous (preferably porous, although it is understood that a non-porous coating layer may be ionically conductive when wetted or moistened by an electrolyte depending on the material comprising the coating layer). For example, a coating layer may be ionically conductive when it also includes an ionically conductive material, e.g., an ionically conductive polymer.

[0036] In some embodiments, the HTMI-polymer-containing coating is a free-standing film or layer: the coating is not placed on a porous polymer base film to form a separator, but instead is the separator itself.

[0037] HTMI-Polymer-Containing Films, Layers, or Coatings The films, layers, or coatings described herein may comprise, consist of, or consist essentially of a high temperature melt-melting (HTMI) polymer. The HTMI polymer is not so limited and may be any polymer with a melting point above 200°C. In a preferred embodiment, the HTMI polymer is a polyamide-imide. In some embodiments, it may be a polyetherimide.

[0038] The polyamide-imide disclosed herein is not particularly limited, and any polyamide-imide not inconsistent with the goals described herein may be used. In some preferred embodiments, the polyamide-imide may be pure polyamide-imide. In some embodiments, the polyamide-imide may be at least one selected from the group consisting of pure polyamide-imide, polyamide-imide with 30% glass fiber, polyamide-imide with 30% carbon fiber, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations thereof.

[0039] In addition to the HTMI polymer, the films, layers, or coatings described herein may include one or more additional components. For example, the films, layers, or coatings may comprise, consist of, or consist essentially of the HTMI polymer and an ion-conducting additive. The ion-conducting additive may, in some embodiments, enable lithium ion transport across the separator when the separators disclosed herein are used in lithium-ion batteries. For example, the ion-conducting additive may be a polymer that becomes ionically conductive when wetted by the electrolyte. In some embodiments, the ion-conducting additive may be PVDF or PVDF-HFP. PVDF is not particularly limited, but some In preferred embodiments, PVDF or PVDF-HFP is soluble in the solvent N-methyl-2-pyrrolidone (NMP) or another solvent in which polyamide-imide is also soluble. Here, soluble means, at least, that polyamide-imide, PVDF, or PVDF-HFP does not precipitate from solution when NMP is used as the solvent for the solution. In some preferred embodiments, PVDF or PVDF-HFP is micron-sized, and in some preferred embodiments, PVDF or PVDF-HFP is micron-sized particles or beads. In some preferred embodiments, PVDF-HFP is used. The HFP content is not particularly limited, but in preferred embodiments, it may be less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, or less than 10%. In some preferred embodiments, the HFP content may be 5% to 30%, preferably 5% to 25%.

[0040] In some preferred embodiments, the films, coatings, or layers described herein comprise, consist of, or consist essentially of polyamide-imide and at least one selected from the group consisting of PVDF, PVDF-HFP, or combinations thereof. Some residual solvent may be present in the final coating, film, or layer.

[0041] In some preferred embodiments, the coating, film, or layer may comprise, consist of, or consist essentially of a HTMI-polymer, such as polyamide-imide, an ion-conducting polymer, such as PVDF, PVDF-HFP, or a combination thereof, and a ceramic, such as alumina. Some residual solvent may also be present in the final coating, film, or layer.

[0042] In some preferred embodiments, the film coatings or layers described herein are produced by a method including preparing a coating slurry or solution. The coating solution may comprise, consist of, or consist essentially of an HTMI polymer, an ion-conducting polymer, and a solvent. The coating slurry may comprise, consist of, or consist essentially of an HTMI polymer, an ion-conducting polymer, a ceramic, and a solvent. In some preferred embodiments, the HTMI polymer is polyamide-imide, the ion-conducting additive is at least one selected from the group consisting of PVDF, PVDF-HFP, and combinations thereof, and the solvent is NMP. In some preferred embodiments, the ceramic is alumina, silica, or an alkali metal salt (e.g., KCl, LiCl). In some embodiments, a solution containing the HTMI polymer and a solution containing the ion-conducting additive may be prepared separately and mixed together to form the coating solution. In other embodiments, a single solution containing the HTMI polymer, the ion-conducting additive, and a solvent may be prepared and used as the coating solution. In some embodiments, a solution containing the HTMI polymer and solvent and a solution containing the ion-conducting polymer may be formed separately, and the ceramic may be added either before or after the solutions are mixed together to form the coating slurry.

[0043] In some embodiments, the method includes the further step of applying a coating slurry or solution to a porous polymeric base film or a substrate or support to form a coating, film, or layer. In embodiments in which a coating slurry or solution is applied to a porous polymeric base film, the coating slurry or solution may be applied to one or both sides thereof. In some embodiments, the coating slurry or solution may be applied to a substrate or support, such as a glass substrate or support, to form a coating on the substrate or support. In embodiments in which the coating slurry or solution is applied to one or both sides of a porous polymer base film, the coated base film may be used as a battery separator. In embodiments in which the coating slurry or solution is applied to a substrate or support, such as a glass substrate, the coating itself may be used as a battery separator.

[0044] In some embodiments, the methods described herein include a further step of removing some, all, or substantially all of the solvent from the coating, film, or layer. In preferred embodiments, all or substantially all of the solvent may be removed from a porous polymer base film or a coating applied to a substrate or support, such as a glass substrate or support. For example, 80% or more, 85% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more, or 100% of the solvent may be removed. In some embodiments, the solvent may be removed by heating the coating for a period of time. For example, in some embodiments, the coating may be heated to 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 75°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher. The heating time may be 1 to 20 hours, 1 to 15 hours, 1 to 10 hours, or 1 to 5 hours. In some preferred embodiments, faster removal of NMP is achieved by heating the coating, film, or layer to a higher temperature. However, acceptable temperatures may be affected by the composition of the polymer base film. A temperature that does not melt or otherwise decompose or destroy the base film should be used. In other embodiments, the solvent may be removed or substantially removed using a process having at least two steps: 1) water chasing and 2) water chasing with air or oven drying overnight at room temperature within ±5 degrees Celsius, which in some preferred embodiments may include immersing the coating, film, or layer in a dip tank containing water or an aqueous solution having more than 50% water, or spraying the coating, film, or layer with water or an aqueous solution having more than 50% water to remove the solvent. The aqueous solution may have more than 50% water and another solvent, such as alcohol or any other solvent. In embodiments where NMP is used as the solvent, PAI is used as the HTMI polymer and PVDF-HFP is used as the ion-conducting additive, and NMP enters the water, leaving the PAI and PVDF-HFP.However, NMP in water may, in some embodiments, carry the polymer (either the HTMI polymer, the ion-conducting polymer, or both) with it. This may leave gaps in the resulting film, layer, or coating. The soak time (or the time the water or aqueous solution remains in contact with the coating, film, or layer) may vary from 1 minute to 1 hour. While not wishing to be bound by any particular theory, it is believed that longer soak times may result in more polymer removal. In a preferred embodiment, a water chasing method is used to recover / recycle the solvent for reuse.

[0045] In some embodiments where a coating slurry containing a ceramic is used, the ceramic may be removed from the coating, film, or layer. In some embodiments, the ceramic does not need to be removed. In embodiments where the ceramic should be removed, i.e., when the ceramic is not compatible with the final battery in which the separator is intended to be used, the ceramic may be removed. For example, a ceramic that is generally not compatible with Li-ion batteries is silica. Silica, when used in a coating slurry, may or should be removed, or may be substantially removed or removed, when the separator is used in a Li-ion battery. One way to remove the silica is by using HF.

[0046] In embodiments where the coating solution or coating slurry is applied directly to, for example, a glass substrate and the solvent is removed or substantially removed, the resulting coating may be removed from the glass substrate and the coating itself may be free-standing and used as a battery separator. In such embodiments, any substrate from which the resulting coating can be easily removed is a good choice for use.

[0047] In some embodiments, the resulting coated polymeric porous base (i.e., separator) after the solvent has been removed or substantially removed has an infinite Gurley and is ionically conductive. In some embodiments, the separator may have a Gurley (seconds / 100 cc) of 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less. While not wishing to be bound by any particular theory, it is believed that the use of ceramics in coatings, films, or layers can result in separators with lower Gurleys. In some embodiments, the resulting coated polymeric porous base (i.e., separator) after the solvent has been removed or substantially removed may have an electrical resistivity (ER) of less than 50, less than 45, less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, less than 5, or less than 3. In some embodiments, the film, coating, or layer may be non-porous (infinite Gurley), substantially non-porous (greater than 7,000 Gurley s / 100 cc), or semi-porous (6,000-7,000 Gurley s / 100 cc), yet ionically conductive due to the presence of at least an ionically conductive additive. In some embodiments, particularly when ceramics are used, the film, coating, or layer may be porous (less than 6,000, less than 5,000, less than 4,000, less than 3,000, less than 2,000, less than 1,000, or less than 500 Gurley s / 100 cc).

[0048] Porous or microporous polymer-based films The porous or microporous polymer base film can be any commercially available separator microporous membrane (e.g., monolayer or multilayer), such as Celgard®, a dry-process product manufactured by Celgard, LLC of Charlotte, North Carolina, or Hipore®, a wet-process product manufactured by Asahi Kasei Corporation of Tokyo, Japan. The base film can have a porosity ranging from 20 to 80%, preferably 30 to 60%, an average pore size ranging from 0.02 to 2 microns, preferably 0.05 to 0.5 microns, a Gurley number ranging from 5 to 150 seconds, preferably 15 to 60 seconds (the Gurley number refers to the time it takes 10 cc of air at 12.2 inches of water (inH2O) to pass through 1 square inch of membrane), and is preferably polyolefinic. Preferred polyolefins include polyethylene and / or polypropylene. Polypropylene may be most preferred (high-temperature polymer, oxidation-resistant).

[0049] The base film or coating substrate may, in some cases, comprise a semi-crystalline polymer, for example, a polymer having a crystallinity in the range of 20 to 80%.

[0050] In some embodiments, the porous or microporous polymer base films described herein may comprise a single layer, two layers, three layers, or multiple layers. For example, a three-layer or multilayer substrate may comprise two outer layers and one or more inner layers. In some cases, the porous or microporous polymer base film may comprise one, two, three, four, five, or more inner layers. As described in more detail below, each of the layers may be coextruded and / or laminated together. may be laminated.

[0051] The porous or microporous polymer base films described herein can be made by a dry stretch process (e.g., the Celgard® dry stretch process described herein) in which one or more polymers are extruded to form the substrate. The outer and inner layers can each be monoextruded, where the layer itself is extruded without any sublayers (plies), or each layer can include multiple coextruded sublayers. For example, each layer can include multiple sublayers, such as coextruded two-sublayer, three-sublayer, or multi-sublayer substrates, each of which can be collectively referred to as a "layer." The number of sublayers in a coextruded two-layer is two, the number of layers in a coextruded three-layer is three, and the number of layers in a coextruded multilayer substrate can be two or more, three or more, four or more, five or more, etc. The exact number of sublayers in a coextruded layer is determined by the die design, and not necessarily the materials that are coextruded to form the coextruded layer. For example, a coextruded two, three, or multi-sublayer substrate may be formed using the same material in each of two, three, four, or more sublayers, which are still considered separate sublayers even though each sublayer is made from the same material.

[0052] In some embodiments, the three-layer or multi-layer porous or microporous polymer-based films described herein can include two outer layers (e.g., a first outer layer and a second outer layer) and a single or multiple inner layers. The multiple inner layers can be monoextruded or coextruded layers. A laminate barrier can be formed between each of the inner layers and / or between each of the outer layers and one of the inner layers. A laminate barrier can be formed when two surfaces, for example, two surfaces of different substrates or layers, are laminated together using heat, pressure, or heat and pressure.

[0053] In some embodiments, the porous or microporous polymer-based films described herein may 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 / PP, 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 / PEPE / PP / PP, PP / PP / PP / PP / PE / PE / PE / PE, PP / PP / PP / PP / PE / PP / PP / PP / PP, PE / PE / PE / PE / PP / PE / PE / PE / PE, PP / PE / PP / PE / PP / PE / PP / PE / PP, PE / PP / PE / PP / PE / PP / PE / PP / PE, PE / PE / PE / PE / PE / PP / PP / PP / PP, PP / PP / PP / PP / PP / PE / PE / PE / PE, PP / PP / PP / PP / PP / PE / PE / PE / PE / PE, PE / PE / PE / PE / PE / PP / PP / PP / PP / PP, PP / PE / PP / PE / PP / PE / PP / PE / PP / PE, PE / PP / PE / PP / PE / PP / PE / PP / PE / PP, PE / PP / PP / PP / PP / PP / PP / PP / PP / PP / PE, PP / PE / PE / PE / PE / PE / PE / PE / PE / PE / PP, PP / PP / PE / PE / PP / PP / PE / PE / PP / PP, P E / PE / PP / PP / PP / PP / PP / PP / PP / PE / PE, PP / PP / PP / PE / PP / PP / PP / PP / PP / PE, or PE / PE / PE / PP / PP / PP / PP / PE / PE / PE / PE / PP / PP. For reference purposes herein, PE represents a single layer within a multi-layer porous or microporous polymer-based film that includes PE. Similarly, PP represents a single layer within a multi-layer porous or microporous polymer-based film that includes PP. Thus, the notation PP / PE represents a two-layer porous or microporous polymer-based film having a polypropylene (PP) layer and a polyethylene (PE) layer. The two layers can be coextruded, or each layer of the two layers can be monoextruded separately and laminated together.

[0054] Each layer in a porous or microporous polymer base film may include multiple sublayers, which may be formed by coextrusion or combining the sublayers to form the individual layers of the multilayer substrate. Using a multilayer porous or microporous polymer base film with a PP / PE / PP structure, each individual PP or PE layer may include two or more coextruded sublayers. For example, when each individual PP or PE layer includes three sublayers, each individual PP layer may be expressed as PP = (PP1, PP2, PP3), and each individual PE layer may be expressed as PE = (PE1, PE2, PE3). Thus, the PP / PE / PP structure may be expressed as (PP1, PP2, PP3) / (PE1, PE2, PE3) / (PP1, PP2, PP3). The composition of each of the PP1, PP2, and PP3 sublayers may be the same, or each sublayer may have a different polypropylene composition from one or both of the other polypropylene sublayers. Similarly, the composition of each of the PE1, PE2, and PE3 sublayers can be the same, or each sublayer can have a different polyethylene composition than one or both of the other polyethylene sublayers. This principle also applies to other multi-layer porous or microporous polymer-based films having more or fewer layers than the exemplary three-layer film above.

[0055] In some embodiments, the porous or microporous polymeric base films described herein have an overall thickness of 1 micron to 60 microns, 1 micron to 55 microns, 1 micron to 50 microns, 1 micron to 45 microns, 1 micron to 40 microns, 1 micron to 35 microns, 1 micron to 30 microns, 1 micron to 25 microns, 1 micron to 20 microns, 1 micron to 15 microns, 1 micron to 10 microns, 5 microns to 50 microns, 5 microns to 40 microns, 5 microns to 30 microns, 5 microns to 25 microns, 5 microns to 20 microns, 5 microns to 10 microns, 10 microns to 40 microns, 10 microns to 35 microns, 10 microns to 30 microns, or 10 microns to 20 microns.

[0056] In some embodiments, each layer in a bi-layer, tri-layer, or multi-layer porous or microporous polymer base film may have a thickness equal to, or less than, or greater than, the thickness of the other layers. For example, when the porous or microporous polymer base film is a tri-layer film including a PP / PE / PP (polypropylene / polyethylene / polypropylene) or PE / PP / PE (polyethylene / polypropylene / polyethylene) structure, the polypropylene layer may have a thickness equal to, less than, or greater than the thickness of the polyethylene layer(s).

[0057] In some embodiments, the porous or microporous polymer base film described herein may be a three-layer laminated PP / PE / PP (polypropylene / polyethylene / polypropylene) or PE / PP / PE (polyethylene / polypropylene / polyethylene) substrate. In some cases, the layer structure ratio of the porous or microporous polymer base film is 45 / 10 / 45%, 40 / 20 / 40%, 39 / 22 / 30%, or 40 / 20 / 40%. 9%, 38 / 24 / 38%, 37 / 26 / 37%, 36 / 28 / 36%, 35 / 30 / 35%, 34.5 / 31 / 34.5%, 34 / 32 / 34%, 33.5 / 33 / 33.5%, 33 / 34 / 33%, 32.5 / 35 / 32.5%, 32 / 36 / 32%, 31.5 / 37 / 31.5%, 31 / 38 / 31%, 30.5 / 39 / 30.5%, 30 / 40 / 30%, 29.5 / 41 / 29.5%, 29 / 42 / 29%, 28.5 / 43 / 28.5%, 28 / 44 / 28%, 27.5 / 45 / 27.5%, or 27 / 46 / 27%.

[0058] The porous or microporous polymer-based films described herein may additionally contain fillers, elastomers, wetting agents, lubricants, flame retardants, nucleating agents, antioxidants, colorants, and / or other additional elements consistent with the scope of the present disclosure. For example, the substrate may contain fillers such as calcium carbonate, zinc oxide, diatomaceous earth, talc, kaolin, synthetic silica, mica, clay, boron nitride, silicon dioxide, titanium dioxide, barium sulfate, aluminum hydroxide, magnesium hydroxide, and the like, or combinations thereof. The elastomer may include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene copolymer (SBR), styrene-isoprene copolymer (SIR), ethylidene norbornene copolymer (ENB), epoxy, and polyurethane, or combinations thereof. The wetting agent may include ethoxylated alcohols, primary polymeric carboxylic acids, glycols (e.g., polypropylene glycol and polyethylene glycol), functionalized polyolefins, and the like. The lubricating oil may include silicone, fluoropolymer, oleamide, stearamide, erucamide, calcium stearate, lithium stearate, or other metal stearates. The flame retardant may include brominated flame retardants, ammonium phosphate, ammonium hydroxide, alumina trihydrate, and phosphoric acid esters. The nucleating agent may include any nucleating agent not inconsistent with the objectives of the present disclosure, such as the beta-nucleating agent for polypropylene disclosed in U.S. Patent No. 6,602,593.

[0059] The porous or microporous polymer base film described in some embodiments herein may be produced by a dry stretching process in some cases. The substrate is understood to be a thin, flexible polymer membrane, film, sheet, foil, or substrate having a plurality of pores extending therethrough. In some cases, the porous substrate is produced by a dry stretching process (also known as the CELGARD® dry stretching process), which refers to a process in which pore formation is obtained by stretching a non-porous, semi-crystalline, extruded polymer precursor in the machine direction (MD), transverse direction (TD), or both MD and TD. For example, see Kesting, Robert E., Synthetic Polymeric Membranes, A, incorporated herein by reference. See Structural Perspective, Second Edition, John Wiley & Sons, New York, NY, (1985), pages 290-297. Such dry stretching processes differ from wet and particle stretching processes. Generally, in wet processes, also known as phase inversion, extraction, or TIPS processes, polymeric materials are mixed with processing oils (sometimes referred to as plasticizers), the mixture is extruded, and pores are formed when the processing oil is removed. These wet process substrates may be stretched before or after the oil is removed, but the principal pore-forming mechanism is the use of processing oils. See, for example, Kesting, Ibid., pages 237-286, which are incorporated herein by reference. Particle stretching processes use particles, such as silica or calcium carbonate, as pore-forming agents. Polymeric materials are mixed with the particles, the mixture is extruded, and pores are formed when the particles are removed. These particle-loaded substrates may be stretched before or after particle removal, although the principle pore-forming mechanism is the use of particles. The porous substrates described herein are, in some cases, preferably made of any Celgard® porous substrate available from Celgard, LLC of Charlotte, NC. ) polyolefin microporous separator substrate.

[0060] The porous polymer base film may be macroporous, mesoporous, microporous, or nanoporous. The porosity of the substrate may be any porosity consistent with the goals of the present disclosure. For example, any porosity that can form an acceptable battery separator is acceptable. In some embodiments, the porosity of the porous substrate is 20-90%, 20-80%, 40-80%, 20-70%, 40-70%, 40-60%, greater than 20%, greater than 30%, or greater than 40%. Porosity is measured using ASTM D-2873 and is defined as the percentage of interstitial space, e.g., pores, in the area of ​​the porous substrate, measured in the machine direction (MD) and transverse direction (TD) of the substrate. In some embodiments, the pores are slit-like and circular, elliptical, trapezoidal, or ovoid with a sphericity factor of 0.25 to 8.0.

[0061] The porous or microporous polymer base film can have any Gurley not inconsistent with the objectives of this disclosure, for example, a Gurley that is acceptable for use as a battery separator. Gurley is a Japanese Industrial Standard (JIS) Gurley and can be measured using a permeability tester, for example, 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 substrate at a constant pressure of 4.9 inches of water (inH2O). In some embodiments, a porous film or substrate described herein has a JIS Gurley (sec / 100cc) of 100 or more, 150 or more, 160 or more, 170 or more, 180 or more, 190 or more, 200 or more, 210 or more, 220 or more, 230 or more, 240 or more, 250 or more, 260 or more, 270 or more, 280 or more, 290 or more, 300 or more, 310 or more, 320 or more, 330 or more, 340 or more, 350 or more, 100 to 800, 200 to 700, 200 to 600, 200 to 500, 200 to 400, 200 to 300, or 300 to 600.

[0062] The porous or microporous polymeric base film, without a coating, can have a high pin puncture strength of 200 gf or greater, 210 gf or greater, 220 gf or greater, 230 gf or greater, 240 gf or greater, 250 gf or greater, 260 gf or greater, 270 gf or greater, 280 gf or greater, 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 400 gf or greater.

[0063] In some embodiments, the porous or microporous polymer base films described herein may contain one or more additives in at least one layer of the porous substrate. In some embodiments, at least one layer of the porous or microporous polymer base film contains more than one additive, for example, 2, 3, 4, 5, or more additives. The additive may be present in one or both outermost layers of the porous substrate, in one or more inner layers, in all of the inner layers, or in both all of the inner layers and the outermost layer. In some embodiments, the additive may be present in one or more outermost layers and one or more innermost layers. In such embodiments, the additive may be released from the outermost layer or layers over time, and the additive supply of the outermost layer or layers may be replenished by migration of the additive in the inner layers to the outermost layer. In some embodiments, each layer of the porous or microporous polymer base film may contain a different additive or combination of additives than adjacent layers of the porous or microporous polymer base film.

[0064] In some embodiments, the additive comprises a functionalized polymer. As will be appreciated by those skilled in the art, a functionalized polymer is a polymer having functional groups originating from the polymer backbone. In some embodiments, the functionalized polymer is a maleic anhydride functionalized polymer. In some embodiments, the maleic anhydride modified polymer is a maleic anhydride functionalized polymer. Examples of suitable polyethylene include 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, and very low density polyethylene.

[0065] In some embodiments, the additive comprises an ionomer. An ionomer, as understood by those skilled in the art, is a copolymer containing both ionic and nonionic repeating groups. The ionic repeating 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.

[0066] In some embodiments, the additive comprises cellulose nanofibers.

[0067] 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.

[0068] In some embodiments, the additive comprises a lubricant. The lubricants or lubricating oils described herein may be any lubricant not inconsistent with the objectives of the present disclosure. As will be 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.

[0069] 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 can 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, where each silicon atom can 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 embodiments described herein, the polysiloxanes can be high molecular weight, e.g., ultra-high molecular weight polysiloxanes. In some embodiments, high and ultra-high molecular weight polysiloxanes can have a weight average molecular weight ranging from 500,000 to 1,000,000.

[0070] The fatty acid salts described herein may be any fatty acid salt consistent with the objectives of the present disclosure. In some cases, the fatty acid salt 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 12 to 22 atoms. For example, the metal fatty acid may be selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, behenic acid, erucic acid, and arachidonic acid. The metal may be any metal consistent with the objectives of the present disclosure. In some cases, the metal is an alkali or alkaline earth metal, such as Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Fr, and Ra. In some embodiments, the metal is Li, Be, Na, Mg, K, or Ca.

[0071] The fatty acid salt may be lithium stearate, sodium stearate, lithium oleate, sodium oleate, sodium palmitate, lithium palmitate, potassium stearate, or potassium oleate.

[0072] Lubricating oils containing the fatty acid salts described herein may have melting points 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 of 220° C.) or sodium stearate (melting point 245-255° C.) have such melting points.

[0073] In some embodiments, the additive may include one or more nucleating agents. As will be understood by those skilled in the art, a nucleating agent is an inorganic material that, in some embodiments, aids in, enhances, or improves the crystallization of a polymer, including a semi-crystalline polymer.

[0074] In some cases, the additive may include a cavitation promoter, which is a material that forms, assists in the formation of, enhances the formation of, or improves the formation of bubbles or voids in a polymer, as understood by those skilled in the art.

[0075] The additive may in some cases include a fluoropolymer, such as those fluoropolymers discussed in detail herein.

[0076] In some embodiments, the additive may include a crosslinking agent.

[0077] The additives described herein can, in some embodiments, include an x-ray detectable material. The x-ray detectable material can be any x-ray detectable material consistent with the objectives of the present disclosure, 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 material or elements are also disclosed in the '510 patent, but in some embodiments, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 20 wt%, up to 10 wt%, up to 5 wt%, or up to 1 wt%, based on the total weight of the porous or microporous polymer-based film, can be used. In one embodiment, the additive is barium sulfate.

[0078] In some embodiments, the additive may include a lithium halide. The lithium halide may be lithium chloride, lithium fluoride, lithium bromide, or lithium iodide. The lithium halide may be lithium iodide, which is both ionically conductive and electrically insulating. In some cases, a material that is both ionically conductive and electrically insulating may be used as part of a porous or microporous polymer base film.

[0079] In some embodiments, the additives may include polymer processing agents. As will be understood by those skilled in the art, 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.

[0080] In some embodiments, the additive can include a high temperature melt-melting (HTMI) polymer. The HTMI polymer can be any HTMI polymer not inconsistent with the objectives of the present disclosure. In some cases, the HTMI polymer can be at least one selected from the group consisting of PMP, PMMA, PET, PVDF, aramid, syndiotactic polystyrene, polyimide, polyamide, and combinations thereof. In some embodiments, the HTMI polymer may be at least one selected from the group consisting of polyamideimides and polyetherimides.

[0081] The additive may optionally include an electrolyte. The electrolyte described herein may be any electrolyte consistent with the objectives of the present disclosure. The electrolyte may be any additive typically added by battery manufacturers, particularly lithium battery manufacturers, to improve battery performance. The electrolyte may also be compatible with, for example, the polymer used in the porous or microporous polymer base film, or compatible with the coating slurry. The compatibility of the additive may also be aided or improved by coating or partially coating the additive. For example, exemplary electrolytes are disclosed in "A Review of Electrolyte Additives for Lithium-Ion Batteries," J. of Power Sources, vol. 162, issue 2, 2006, pp. 1379-1394, which is incorporated herein by reference in its entirety. In some embodiments, the electrolyte is at least one selected from the group consisting of a solid electrolyte interphase (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 improver, an aluminum corrosion inhibitor, a wetting agent, and a thickener. In some embodiments, the electrolyte can have more than one property, for example, it can be a wetting agent and a thickener.

[0082] Exemplary SEI improvers include VEC (vinyl ethylene carbonate), VC (vinylene carbonate), FEC (fluoroethylene carbonate), and LiBOB (lithium bis(oxalato)borate). Exemplary cathode protectants include N,N'-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 ionic solvation improvers include 12-crown-4 and TFPPB (tris(pentafluorophenyl)). Exemplary Al corrosion inhibitors include LiBOB and LiODFB, e.g., borate salts. Exemplary wetting agents and viscosity reducers include cyclohexane and P2O5.

[0083] In some embodiments, the electrolyte additive is air stable or resistant to oxidation. Battery separators containing the electrolyte additives disclosed herein may have a shelf life of several weeks to several months, e.g., 1 week to 11 months.

[0084] In some embodiments, the additive may comprise an energy-dissipating immiscible additive, where immiscible means that the additive is not miscible with the polymer used to form the layer of the porous or microporous polymer-based film containing the additive.

[0085] The porous or microporous polymer base films described herein can be MD or TD stretched to make the film porous. In some cases, the porous or microporous polymer base films are produced by sequentially stretching a MD-stretched substrate in the TD direction, or sequentially stretching a TD-stretched substrate in the MD direction. In addition to sequential MD-TD stretching (with or without relaxation), the substrate can also undergo simultaneous biaxial MD-TD stretching (with or without relaxation). Furthermore, simultaneous or sequential MD-TD stretched porous substrates can be followed by sequential stretching, relaxation, heat setting, or calendaring steps to reduce substrate thickness, reduce roughness, reduce percent porosity, increase TD tensile strength, increase uniformity, and / or reduce TD tearing.

[0086] In some embodiments, the porous or microporous polymer base film has a micron-to-micron ratio of 0.01 nm to 1 micron, 0.01 micron to 1 micron, 0.02 micron to 1 micron, 0.03 micron to 1 micron, 0.04 micron to 1 micron, 0.05 micron to 1 micron, 0.06 micron to 1 micron, 0.07 micron to 1 micron, 0.08 micron to 1 micron, 0.09 micron to 1 micron, 0.1 micron to 1 micron, 0.2 micron to 1 micron, 0.3 micron to 1 micron, 0.4 micron to 1 micron, 0.5 micron to 1 micron, 0.6 micron to 1 micron, 0.7 micron to 1 micron, 0.8 micron to 1 micron, 0.9 micron to 1 micron, 0.01 micron to 0.9 micron, 0.01 micron to 0.8 micron, 0.01 micron to 0.7 micron, 0.01 micron to 0.6 micron, 0.01 micron Kron ~ 0.5 microns, 0.01 microns ~ 0.4 microns, 0.01 microns ~ 0.3 microns, 0.01 microns ~ 0.2 microns, 0.01 microns ~ 0.1 microns, 0.01 microns ~ 0.09 microns, 0.01 microns ~ 0.08 microns, 0.01 microns ~ 0.07 microns, 0.01 microns ~ 0.06 microns, 0.01 microns ~ 0.05 microns, 0.01 microns ~ 0.04 microns, 0.01 The porous membrane may comprise pores having an average pore size of between 0.03 microns, 1 micron, 0.9 microns, 0.8 microns, 0.7 microns, 0.6 microns, 0.5 microns, 0.4 microns, 0.3 microns, 0.2 microns, 0.1 microns, 0.09 microns, 0.08 microns, 0.07 microns, 0.06 microns, 0.05 microns, 0.04 microns, 0.03 microns, 0.02 microns, or 0.01 microns.

[0087] In certain embodiments, porous or microporous polymer base films can be produced using exemplary processes including stretching and sequential calendaring steps, e.g., longitudinal stretching followed by transverse stretching (with or without longitudinal relaxation), and sequential calendaring steps to controllably reduce the thickness of such stretched substrates, e.g., multilayer porous substrates, to controllably reduce the percent porosity of such stretched substrates, e.g., multilayer porous or microporous polymer base films, and / or to controllably improve the strength, properties, and / or performance of such stretched substrates, e.g., multilayer porous substrates, such as the pin puncture strength, longitudinal and / or transverse tensile strength, uniformity, wettability, coatability, workability, compression, springback, twist, permeability, thickness, pin removal force, mechanical strength, surface roughness, hot tip hole propagation, and / or combinations thereof, of such stretched substrates, e.g., multilayer porous substrates, and / or as a method for producing unique structures, pore structures, materials, substrates, base substrates, and / or separators.

[0088] In some cases, the TD tensile strength of multilayer porous or microporous polymer base films can be further improved by adding a calendering process followed by TD stretching. The calendering process typically involves heat and pressure, which can reduce the thickness of the porous substrate. The calendering process can recover the loss of MD and TD tensile strength caused by TD stretching. Furthermore, the increase observed in MD and TD tensile strength by calendering can create a more balanced MD and TD tensile strength ratio, which can be beneficial to the overall mechanical performance of multilayer porous or microporous polymer base films.

[0089] The calendering process selectively densifies the heat-sensitive material using uniform or non-uniform heat, pressure, and / or speed, and provides 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 processes, multiple-roll processes, or combinations thereof) to produce or control improved, desired, or unique structures, characteristics, and / or performance. In some embodiments, calendering temperatures of 50°C to 70°C and line speeds of 40 to 80 ft / min can be used, with calendering pressures of 50 to 200 psi. Higher pressures can, in some cases, result in thinner separators, while lower pressures result in thicker separators.

[0090] In some embodiments, the porous or microporous polymer-based films described herein can include a coating located on a first side, a second side, or both the first and second sides of the porous substrate, as shown schematically in FIG.

[0091] According to at least selected embodiments, this disclosure or invention is preferably directed to polyamide-imide-coated membranes, separator films, or separators for lithium batteries, e.g., high-energy or high-voltage rechargeable lithium batteries and corresponding batteries. In certain embodiments, the battery may be a Li-metal battery, a sodium battery, or a sulfur battery. The separator preferably includes a porous or microporous polyamide-imide coating or layer on at least one side of a polymeric microporous layer, membrane, or film. The polyamide-imide coating or layer may include other polymers, additives, fillers, etc. The polyamide-imide coating may be adapted, for example, to impart oxidation resistance, inhibit dendrite growth, add dimensional and / or mechanical stability, reduce shrinkage, add high-temperature performance (HTMI functionality), prevent electronic shorts at temperatures above 200°C, etc. The microporous polymer substrate may be adapted to at least retain a liquid, gel, or polymer electrolyte, conduct ions, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown function). The polyamide-imide coated separator may be adapted, for example, to keep the electrodes apart at high temperatures, provide oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high temperature performance (HTMI function), prevent electronic shorting at temperatures above 200°C, increase pin puncture strength, and / or prevent ion flow between the anode and cathode in the event of thermal runaway (shutdown function). While secondary lithium battery applications may be preferred, the polyamide-imide coated membrane may be used as a layer or component in batteries, cells, primary batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or other applications, devices, etc.

[0092] According to at least certain embodiments, the separator has at least one polyamide-imide coating or layer containing at least a polyamide-imide and one or more pore-formers (e.g., plasticizers, solvents, antisolvents, particles, or polymers), and can be made semi-porous or porous by removing at least some of the pore-formers from a coating formulation of at least a polyamide-imide and a pore-former, a polyamide-imide, another polymer and a pore-former, or a polyamide-imide, a polymer and a pore-former.

[0093] According to at least selected embodiments, the separator has at least one polyamide-imide coating or layer containing at least polyamide-imide and one or more other polymers or copolymers, and is non-porous (especially when thin or when the electrolyte The polyamide-imide coating or layer may be semi-porous, microporous, nanoporous, or porous (still ionically conductive in the electrolyte when containing PVDF, PVDF:HFP, and / or other polymers or materials that are wet, filled, swollen, or gelled). While the polyamide-imide coating or layer may be continuous, it may be preferable to use discontinuous or broken patterns, dots, islands, stripes, etc. For example, densely packed dots may be digitally printed onto the base film or substrate. The coating and base film may also be co-extruded, cascade cast, co-stretched, co-extruded, etc.

[0094] According to at least certain selected embodiments, a polyamide-imide coated separator for a high energy or high voltage rechargeable lithium battery comprises: a solid-state electrolyte (SSE) layer or substrate, and A polyamide-imide coating or layer on at least one side of the SSE layer Includes:

[0095] According to at least certain other embodiments, the separator has at least one polyetherimide coating or layer instead of a polyamide-imide layer.

[0096] According to at least selected embodiments, aspects, or objectives, new or improved coated membranes, coated materials, coatings, separators, coated separators, polyamide-imide coated membranes, separator membranes, or separators are provided for lithium batteries, e.g., high-energy or high-voltage rechargeable lithium batteries, and corresponding batteries, including those shown, described, or claimed herein. The batteries may be lithium batteries, lithium-ion batteries, lithium polymer batteries, lithium secondary batteries, lithium-ion rechargeable batteries, Li metal (anode) batteries, Li-sulfur (Li-S) batteries, Li SSE batteries, Li metal SSE batteries, sodium SSE batteries, sulfur SSE batteries, sodium-sulfur (NaS) batteries, Li iron disulfide (Li / FeS) batteries, graphite (cathode) batteries, Li metal (anode) graphite (cathode) batteries, sodium batteries, NMC or NCM batteries, capacitors, etc. In at least certain embodiments, the polyamide-imide coated membranes are adapted to be wetted by a liquid electrolyte, filled with a gel electrolyte, etc. In at least certain other embodiments, at least the polyamide-imide coating or coatings are adapted to be wetted by a liquid electrolyte, to be filled by a gel electrolyte, or the like.

[0097] In accordance with at least certain embodiments, aspects, or objectives, issues, problems, or drawbacks of certain prior separators are addressed by the present new or improved coated membranes, coated materials, coatings, separators, coated separators, polyamide-imide coated membranes, separator membranes, or separators for lithium batteries, e.g., high energy or high voltage rechargeable lithium batteries, and corresponding batteries, including those as shown, described, or claimed herein.

[0098] In some embodiments, the coating can include a first layer and a second layer. In some cases, the first layer of the coating can be positioned on the first side of the substrate, the second side of the substrate, or both the first and second sides of the substrate. When the first layer is positioned on the first and / or second side of the substrate, the second layer of the coating can be positioned on one or both of the first layer(s) of the coating.

[0099] In some embodiments, the second layer of the coating is on the first side of the substrate, the second side of the substrate , or may be positioned on both the first and second sides of the substrate. When the second layer is positioned on the first and / or second sides of the substrate, the first layer of coating may be positioned over one or both of the second layers of coating.

[0100] In a further embodiment, a first layer of the coating may be positioned on one of the first or second sides of the substrate, and a second layer of the coating may be positioned on the other of the first or second sides of the substrate, in which the first layer on one of the sides of the substrate may optionally be covered by a second layer, and the second layer on the other side of the substrate may optionally be covered by a first coating, resulting in opposite coating layer configurations on the first and second sides.

[0101] Furthermore, in other embodiments, a first layer may be located on both the first and second sides of the substrate, with only one of the two first layers on the substrate being further covered by a second layer of coating. Similarly, in other cases, a second layer may be located on both the first and second sides of the substrate, with only one of the two second layers on the substrate being further covered by a first layer of coating.

[0102] The first and second layers may each have any thickness consistent with the objectives of the present disclosure. In some cases, the first layer has a thickness of 10 nm to 20 microns, 500 nm to 15 microns, 500 nm to 10 microns, 500 nm to 5 microns, or 500 nm to 1 micron. The second layer may have a thickness of 500 nm to 20 microns, 500 nm to 15 microns, 500 nm to 10 microns, 500 nm to 5 microns, or 500 nm to 1 micron. The thicknesses of the first and second layers may be the same or different.

[0103] In another embodiment, a method of preparing the coated separator described above includes coating a first surface, an opposing second surface, or both the first and second surfaces of a porous substrate with a layer, a first layer, and / or a second layer.

[0104] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics, and therefore, reference should be made to the claims, drawings, or specification as indicating the scope of the invention. [Example]

[0105] Examples 1 and 2: As a first step, a coating solution was prepared by combining PVDF-HFP with less than 20% HFP and polyamide-imide (Solvay Torlon) in NMP. The solution was amber but clear, which is surprising because polyimide and PVDF are typically not miscible, as demonstrated in Comparative Example 2.

[0106] The coating solution was then coated onto one side of a porous polymer base film. In this example, Celgard® 2500PP base film was used. After coating, there are two methods for removing the NMP. One is oven drying, and the other is NMP extraction in a water bath followed by air drying. The latter method is preferred because it is faster, more effective, and results in better film formation. Figure 2 shows the overall laboratory coating process using the water extraction process.

[0107] Two separate samples were prepared using different NMP removal methods. The resulting separator (base film + coating) thickness and Gurley (sec) were measured and visually evaluated. The results were determined visually at 15x magnification. The results are presented in Figure 3. As shown in Figure 3, the water immersion method produced a smoother coating than the oven-dry method. Both films had infinite Gurley.

[0108] Examples 3 to 5 The coating solutions were prepared in the same manner as in Examples 1 and 2. In Examples 3 and 4, the PAI / PVDF ratios are shown in the table in Figure 4 below. In Examples 3-5, the coatings were applied to Celgard® 2500 as a base film. In each of Examples 3-5, the solvent (NMP) was removed by air-drying overnight using the water-chasing method. The immersion time was varied between 2 and 5 minutes. As shown in the table in Figure 4, a longer immersion time of 5 minutes produced a lower Gurley coating. The ER of Example 4 is also reported to be lower than that of Example 3, but has not yet been measured. The table in Figure 4 also shows that a higher PAI / PVDF ratio results in a film with a lower ER (compare Examples 3 and 5 with the same water immersion time). Comparative Example 1 shows the shrinkage and ER of an uncoated 2500 base film. The ER of the coated film was measured by immersing the coated film in electrolyte for 1 hour to swell the PVDF. SEMs of the base film and the coated base film are provided in Figures 5A and 5B.

[0109] Figure 6 shows that Example 5 is wettable by the electrolyte solvent, propylene carbonate (PC), as indicated by areas that become clear.

[0110] Examples 6 and 7 and Comparative Example 2.

[0111] Examples 6-8 and Comparative Example 2 were prepared similarly to Examples 1 and 2, except that polyimide (PI) was used instead of polyamide-imide (PAI) in Comparative Example 2. Solvent removal or substantial removal was achieved as shown in the table in Figure 7 below. SEM of these examples shows that the water immersion process produces the smoothest coating, which is more preferable for battery separators. Compare Examples 6 and 7. It also shows that films formed using PI instead of PAI do not work. PI is not miscible with PVDF at all. This is shown even by the appearance of the coating to the naked eye. Compare Comparative Example 2 and Example 6. See Figure 7.

[0112] Non-limiting example lithium battery description: Cylindrical lithium iron disulfide batteries use lithium as the anode and iron disulfide as the cathode, with a lithium salt in an organic solvent blended with the electrolyte. A cross section (Figure 8) of a typical cylindrical LiFeS2 battery is shown in the figure below:

Claims

1. 1. A polyamide-imide coated separator for a high energy or high voltage rechargeable lithium battery comprising: a microporous polymer layer, membrane or film, and a polyamide-imide coating or layer on at least one side of said microporous polymer layer A polyamide-imide coated separator comprising:

2. 10. The separator of claim 1, wherein the polyamide-imide coating or layer may be adapted to impart oxidation resistance, inhibit dendrite growth, add dimensional stability, reduce shrinkage, add high temperature capability (HTMI functionality), prevent electronic shorting at temperatures above 200°C, etc.

3. 3. The separator of claim 1 or 2, wherein the microporous polymer layer may be adapted to retain a liquid electrolyte, to conduct ions, and / or to prevent ion flow between the anode and cathode of a cell or battery in the event of thermal runaway (i.e., shutdown functionality).

4. 4. The separator of claim 1, wherein the polyamide-imide coating or layer is non-porous, semi-porous, porous, microporous, mesoporous, macroporous, and / or nanoporous.

5. 5. The separator of claim 4, wherein the polyamide-imide coating or layer may be made porous by removing plasticizers, pore formers, and / or particles from a coating formulation of at least polyamide-imide and at least one of plasticizers, pore formers, particles, or combinations thereof.

6. 6. The separator of claim 5, wherein the polyamide-imide coating or layer contains at least polyamide-imide and particles or polymers and may be made semi-porous or porous by removing at least some of the particles from a coating formulation of at least polyamide-imide and particles, polyamide-imide, another polymer and particles, or polyamide-imide, polymer and particles.

7. 7. The separator according to claim 5 or 6, wherein the particles or polymers are selected from PVDF, PVDF-HFP, others that are ion-conductive, or mixtures thereof.

8. The separator of any one of claims 5 to 7, wherein the inorganic or ceramic particles are also part of the coating formulation and may or may not be removed.

9. The separator of any one of claims 5 to 8, wherein the particles, including the inorganic or ceramic particles, may be removed by one or more solvents.

10. 10. The separator of claim 9, wherein the one or more solvents are water, an aqueous solvent, HF, or a mixture thereof.

11. The separator according to any one of claims 5 to 7, wherein the particles are solvent-soluble particles or polymers, or are not solvent-soluble particles or polymers.

12. The polyamide-imide coating or layer may contain a plasticizer at least in part in the polyamide-imide.

6. The separator of claim 5, which may be made semi-porous or porous by removing the mide and plasticizer from the coating formulation.

13. 6. The separator of claim 5, wherein the polyimide coating or layer may be made semi-porous or porous by removing the pore former from a coating formulation of at least polyamide-imide and pore former.

14. The separator of any one of claims 1 to 13, wherein the polyamide-imide coating or layer may include other polymers, additives, fillers, etc.

15. 15. The separator according to any one of claims 1 to 14, wherein the polyamide-imide of the polyamide-imide coating or layer is selected from the group consisting of pure polyamide-imide, polyamide-imide with 30% glass fiber, polyamide-imide with 30% carbon fiber, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations thereof.

16. The separator of any one of claims 1 to 15, wherein the polyamide-imide of the polyamide-imide coating or layer is pure polyamide-imide.

17. 16. The separator of any one of claims 1 to 15, wherein the polyamide-imide coating or layer is selected from the group consisting of 30% glass fiber polyamide-imide, 30% carbon fiber polyamide-imide, carbon fiber-containing polyamide-imide, graphite-containing polyamide-imide, and combinations thereof.

18. The separator of any one of claims 5 to 10, wherein the particles comprise between 20% and 80% by weight of the polyamide-imide and particle mixture before being removed.

19. The separator according to any one of claims 1 to 18, wherein the microporous polymer layer is a polyolefin membrane.

20. 20. The separator of claim 19, wherein the polyolefin membrane is a polypropylene and / or polyethylene-containing membrane.

21. 20. The separator of claim 19, wherein the polyolefin membrane has a porosity in the range of 20 to 80%, an average pore size in the range of 0.02 to 1.0 microns, and a Gurley number in the range of 5 to 500 seconds.

22. The separator of any one of claims 5 to 7, wherein the particles have an average particle size in the range of 0.001 to 10 microns.

23. 23. A high energy or high voltage rechargeable lithium battery comprising: an anode; a cathode; the separator of any one of claims 1 to 22 disposed between the anode and the cathode; and an electrolyte in ionic communication with the anode and the cathode through the separator.

24. 23. A high-energy rechargeable lithium battery comprising: an anode containing lithium metal or a lithium alloy or a mixture of lithium metal and / or a lithium alloy with another material; a cathode; a separator according to any one of claims 1 to 22 disposed between the anode and the cathode; and an electrolyte in ionic communication with the anode and the cathode through the separator.

25. 1. A polyamide-imide coated membrane adapted for high energy or high voltage rechargeable lithium batteries, batteries, cells, primary batteries, secondary batteries, capacitors, fuel cells, textiles, filters, and / or composites, and / or as a layer or component in other applications, devices, etc., comprising: a microporous substrate, membrane or film, and a polyamide-imide coating or layer on at least one side of said microporous substrate, membrane or film, wherein said microporous substrate, membrane or film is a polymer layer, more preferably a polyolefin layer, most preferably a polyolefin layer of a dry stretch process; 1. A polyamide-imide coated membrane comprising:

26. 1. A polyamide-imide coated separator for a high energy or high voltage rechargeable lithium battery comprising: a microporous polymer layer, membrane or film, and a polyamide-imide coating or layer on at least one side of the microporous polymer layer, the separator having a Gurley coefficient of infinity or less, an electrical resistivity (Ω-cm) of 30 or less; ２ ) or both; A polyamide-imide coated separator comprising:

27. 27. The separator of claim 26, wherein the separator has a Gurley (sec / 100cc) of infinity or less, preferably 7,000 or less, more preferably 6,000 or less, 5,000 or less, 4,000 or less, 3,0000 or less, 2,000 or less, 1,000 or less, or 500 or less.

28. The separator has an electrical resistance (Ω-cm) of 30 or less, more preferably 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less. ２ 27. The separator of claim 26, comprising:

29. 27. The separator of claim 26, wherein the separator has both a Gurley (sec / 100 cc) of infinity or less, preferably 7,000 or less, more preferably 6,000 or less, 5,000 or less, 4,000 or less, 3,0000 or less, 2,000 or less, 1,000 or less, or 500 or less, and an electrical resistance of 30 or less, more preferably 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less.

30. The separator according to any one of claims 26 to 29, wherein the polyamide-imide coating layer comprises polyamide-imide and an ion-conducting additive.

31. 31. The separator of claim 30, wherein the ion-conducting additive is an ion-conducting polymer.

32. 32. The separator of claim 31, wherein the ion-conducting polymer is at least one selected from the group consisting of PVDF, PVDF-HFP, and combinations thereof.

33. 33. The separator of claim 32, wherein the ion-conducting polymer is PVDF-HFP with a percentage of HFP between 5-35%, less than 30%, less than 25%, less than 20%, less than 15%, or less than 10%.

34. The polyamide-imide coating or layer comprises: A coating solution containing polyamide-imide, an ion-conductive polymer, and a solvent is prepared. forming a film or layer or coating by applying to at least one side of the microporous polymer layer, membrane or film, or by applying a coating slurry comprising a polyamide-imide, an ion-conducting polymer, a ceramic, and a solvent to at least one side of the microporous polymer layer, membrane or film; and removing or substantially removing the solvent from the film, coating, or layer using oven heating or by immersing or spraying the film, layer, or coating with aqueous or pure water to extract the solvent, and then drying the film or layer; The separator of any one of claims 25 to 33, formed by a method comprising:

35. 35. The separator of claim 34, wherein the aqueous solution comprises more than 50% water, preferably 100% water.

36. 35. The separator of claim 34, wherein the solvent is removed or substantially removed from the film or layer by immersing or spraying the film, layer, or coating with an aqueous solution or 100% water to extract the solvent, and then drying the film or layer.

37. 37. The separator of claim 36, wherein the film or layer is immersed in or contacted with the aqueous solution or 100% water for a period of from 1 second to 30 minutes.

38. 38. The separator of claim 36 or 37, wherein the aqueous solution comprises more than 50% water, preferably 100% water.

39. 35. The separator of claim 34, wherein the ion-conducting polymer is at least one selected from the group consisting of PVDF, PVDF-HFP, or a combination thereof.

40. 35. The separator of claim 34, wherein the solvent is NMP or another solvent that can dissolve polyamide-imide and / or can be extracted using water or an aqueous solution.

41. The ceramic is SiO ２ 35. The separator of claim 34, wherein the ceramic is at least one selected from the group consisting of: alumina, alkali metal salts (such as KCl, LiCl, etc.), and combinations thereof, and wherein the ceramic may or may not be removed from the film, layer, or coating.

42. 1. A polyamide-imide separator for a high energy or high voltage rechargeable lithium battery comprising: Freestanding polyamide-imide layer or film comprising, consisting of, or consisting essentially of polyamide-imide and at least one ion-conducting additive A polyamide-imide separator comprising:

43. 43. The separator of claim 42, wherein the polyamide-imide is selected from the group consisting of pure polyamide-imide, polyamide-imide with 30% glass fiber, polyamide-imide with 30% carbon fiber, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations thereof.

44. 44. The separator of claim 42 or 43, wherein the ion-conducting additive is an ion-conducting polymer.

45. 45. The separator of claim 44, wherein the ion-conducting polymer is at least one selected from the group consisting of PVDF, PVDF-HFP, and combinations thereof.

46. 46. ​​The separator of claim 45, wherein the ion-conducting polymer is PVDF-HFP and the HFP content is between 5 and 35%.

47. 47. The separator of any one of claims 42-46, wherein the separator has a Gurley (sec / 100cc) of less than or equal to infinity, an electrical resistance of less than or equal to 30, or both.

48. 48. The separator of claim 47, wherein the separator has a Gurley (sec / 100cc) of infinity or less, preferably 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less.

49. 48. The separator of claim 47, wherein the separator has an electrical resistance of 30 or less, preferably 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less.

50. 48. The separator of claim 47, wherein the separator has both a Gurley (sec / 100cc) of infinity or less, preferably 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less, and an electrical resistance of 30 or less, preferably 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less.

51. The HTMI-polymer layer comprises: forming a layer or film by applying a coating solution comprising a polyamide-imide, an ion-conducting polymer, and a solvent to a support, e.g., a glass substrate, or by applying a coating slurry comprising a polyamide-imide, an ion-conducting polymer, a solvent, and a ceramic to a support, e.g., a glass substrate; and removing or substantially removing the solvent from the layer using oven heating or by immersing or spraying the film or layer with an aqueous solution to extract the solvent, and then drying the film or layer; 43. The separator of claim 42 formed by a method comprising:

52. 52. The separator of claim 51, wherein the aqueous solution comprises more than 50% water, preferably 100% water.

53. 52. The separator of claim 51, wherein the polyamide-imide is selected from the group consisting of pure polyamide-imide, 30% glass fiber polyamide-imide, 30% carbon fiber polyamide-imide, polyamide-imide with carbon fiber, polyamide-imide with graphite, and combinations thereof.

54. The separator according to any one of claims 51 to 53, wherein the ion-conducting additive is an ion-conducting polymer.

55. The ion-conductive polymer is PVDF, PVDF-HFP, or a combination thereof.

55. The separator of claim 54, wherein the separator is at least one selected from the group consisting of:

56. 56. The separator of claim 55, wherein the ion-conducting polymer is PVDF-HFP with an HFP content between 5 and 35%.

57. 52. The separator of claim 51, wherein the solvent is removed or substantially removed by immersing the layer in an aqueous solution or spraying the layer with an aqueous solution to extract the solvent, and then drying the layer.

58. 58. The separator of claim 57, wherein the layer is immersed in the aqueous solution for 1 second to 30 minutes.

59. The ceramic is SiO ２ 52. The separator of claim 51, wherein the ceramic is at least one selected from the group consisting of: alumina, alkali metal salts (such as KCl, LiCl, etc.), and combinations thereof, wherein the ceramic may or may not be removed to form the final film or layer.

60. 59. The separator of claim 51, claim 57 or claim 58, wherein the solvent is NMP or another solvent that can dissolve polyamide-imide and / or be extracted by water or an aqueous solution.

61. 10. The separator of claim 1, wherein the polyamide-imide coating or layer contains at least a polyamide-imide and one or more pore-forming agents (e.g., a plasticizer, a solvent, an antisolvent, a particle, or a polymer) and may be made semi-porous or porous by removing at least some of the pore-forming agents from a coating formulation of at least polyamide-imide and pore-forming agent, polyamide-imide, another polymer and pore-forming agent, or polyamide-imide, a polymer and pore-forming agent.

62. 10. The separator of claim 1, wherein the polyamide-imide coating or layer contains at least polyamide-imide and one or more other polymers or copolymers and may be non-porous (still ionically conductive in the electrolyte), semi-porous, microporous, nanoporous, or porous.

63. 1. A polyamide-imide coated separator for a high energy or high voltage rechargeable lithium battery comprising: a solid electrolyte (SSE) layer or substrate, and a polyamide-imide coating or layer on at least one side of the SSE layer; A polyamide-imide coated separator comprising:

64. 1. A polyamide-imide separator for a high energy or high voltage rechargeable lithium battery comprising: At least one layer of at least polyamide-imide, polyamide-imide and a pore former, polyamide-imide, another polymer and a pore former, and / or polyamide-imide, another polymer and a pore former. A polyamide-imide separator comprising:

65. The separator of any one of claims 1 to 64, wherein polyetherimide is used instead of polyamide-imide.

66. Lithium batteries, e.g., high energy or high voltage rechargeable lithium batteries, including those similar to those shown, described, or claimed herein , and new or improved coated membranes, coated materials, coatings, separators, coated separators, polyamide-imide coated membranes, separator membranes, polyamide-imide layers, or separators for corresponding batteries.

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