Improved separator for lead-acid batteries, improved battery and related methods

Abstract

To provide an improved separator capable of improving a cycle life, suppress antimony poisoning, reduce water consumption, reduce a float charging current, and / or reduce a voltage required for re-charging completely the battery.SOLUTION: The present specification discloses an improved separator for a lead-acid battery, an improved battery, and a related method. The separator may contains a porous film, a rubber and / or latex, at least one performance improvement additive agent or a surface active agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to and benefit of International Patent Application No. PCT / US2016 / 035285, filed June 1, 2016.

[0002] According to at least selected embodiments, the present disclosure or invention relates to new or improved separators for flooded lead-acid batteries, particularly lead-acid batteries such as enhanced flooded lead-acid batteries ("EFB"), and various other lead-acid batteries such as gel batteries and absorbed glass mat ("AGM") batteries. According to at least selected embodiments, the present disclosure or invention relates to new or improved separators, battery separators, EFB separators, batteries, cells, systems, methods including same, vehicles using same, methods of manufacturing same, uses of same, and any combination thereof. Also disclosed herein are methods, systems, and battery separators for extending battery life, reducing battery failure, reducing water loss, improving oxidation stability, improving, maintaining, and / or lowering float current, improving end-of-charge ("EOC") current, reducing the current and / or voltage required to charge and / or fully charge a deep-cycle battery, minimizing internal electrical resistance, lowering electrical resistance, increasing wettability, reducing electrolyte wet-out time, shortening battery formation time, inhibiting antimony poisoning, inhibiting acid stratification, improving acid diffusion, and / or improving lead-acid battery uniformity, and any combination thereof. According to at least certain embodiments, the present disclosure or invention relates to improved separators for lead-acid batteries, including rubber, latex, and / or improved performance-enhancing additives and / or coatings. According to at least certain embodiments, the disclosed separators are useful in deep-cycle applications, such as transportation vehicles, such as golf carts (sometimes called golf cars), inverters, and renewable and / or alternative energy systems, such as solar and wind power systems. The disclosed separators are also useful in battery systems where deep cycling and / or partial state of charge operation is part of the battery's use. In certain other embodiments, the disclosed separators can be used in battery systems where additives and / or alloys (antimony being a prime example) are added to the battery to extend the battery's life and / or improve the battery's performance and / or improve the battery's deep cycling and / or partial state of charge operation capabilities. [Background technology]

[0003] Battery separators are used to separate the positive and negative electrodes (plates) of a battery to prevent electrical shorts. Such battery separators are typically microporous to allow ions to pass between the positive and negative electrodes (plates). In lead-acid batteries, such as vehicle batteries, industrial batteries, and / or deep-cycle batteries, battery separators are typically microporous polyethylene separators; in some examples, such separators may include a backweb and a plurality of upstanding ribs on one or both sides of the backweb. See Besenhard, J.O., Editor, Handbook of Battery Materials, Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), Chapter 9, pp. 245-292. Some separators for vehicle batteries are manufactured in continuous lengths, rolled, folded, and sealed along the edges to form a pouch or envelope that receives the battery electrodes. Certain separators for industrial (traction or deep cycle storage) batteries are cut to approximately the same size as the electrode plates (segments or leaves).

[0004] Lead-acid battery electrodes are often made from lead alloys with relatively high antimony content. Lead / antimony alloys have advantages both in the manufacturing process of the electrode frame (improving the flow characteristics of the molten metal in the mold and increasing the hardness of the cast electrode frame, to name just a few) and during use in the battery. Particularly in the case of cyclic loading, good contact between the terminal and the active material is ensured in the positive electrode, in addition to mechanical stability, resulting in no premature capacity loss (the "antimony-free" effect) and improved cyclability. Also, in deep-cycle batteries, antimony is often present in the positive lattice of the battery.

[0005] However, antimony-containing positive electrodes have the disadvantage that antimony can ionically dissolve in the electrolyte and then migrate through the separator. Because antimony is more noble than lead, it can precipitate on the negative electrode. This process is described as antimony poisoning. Antimony poisoning increases water consumption through a reduction in hydrogen overpotential, resulting in batteries requiring more maintenance. In particular, antimony can reduce charging voltage by catalyzing water decomposition, which can consume some of the energy required to fully recharge the battery. Attempts to completely or partially replace antimony in lead alloys with other alloying elements have already been made, but have not yielded satisfactory results. Overall, the presence of antimony in the positive lattice of deep-cycle batteries may represent a major cause of reduced cycle life.

[0006] There is a need for improved separators that, at least for certain applications or batteries, improve cycle life, reduce antimony poisoning, reduce water consumption, reduce float charge current, and / or reduce the voltage required to fully recharge a battery. More specifically, there is a need for improved separators that extend battery life, reduce battery failure, reduce water loss, improve oxidative stability, improve, maintain, and / or reduce float current, improve end-of-charge ("EOC") current, reduce the current and / or voltage required to charge and / or fully charge a deep cycle battery, minimize internal electrical resistance increase, reduce electrical resistance, increase wettability, reduce electrolyte wet-out time, reduce battery formation time, reduce antimony poisoning, reduce acid stratification, improve acid diffusion, and / or improve uniformity in lead-acid batteries, and for improved batteries (such as golf car batteries or golf cart batteries) with the improved separators. Summary of the Invention [Problem to be solved by the invention]

[0007] Details of one or more embodiments are set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims. According to at least selected embodiments, the present disclosure or invention may address the problems or needs described above. According to at least certain objects, aspects, or embodiments, the present disclosure or invention may provide improved separators and / or batteries that overcome the above-mentioned problems, for example, by providing batteries with reduced antimony poisoning and improved cycling performance. [Means for solving the problem]

[0008] According to at least selected embodiments, the present disclosure or invention relates to new or improved separators, cells, batteries, systems, and / or methods of making and / or using such new separators, cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention relates to new or improved battery separators for tubular or flat plate lead acid batteries, including batteries for deep cycle and / or motive applications such as golf carts (sometimes called golf cars), or for solar or wind power systems, and / or improved methods of making and / or using such improved separators, cells, batteries, systems, etc. Also included herein are novel or improved separators and / or batteries for, among other things, extending battery performance and life beyond 50% of the native or intended battery life, reducing battery failure, reducing water loss, improving oxidative stability, improving, maintaining, and / or lowering float current, improving end-of-charge current, and / or improving battery life. Disclosed are methods, systems, and battery separators for improving the electrical conductivity of lead-acid batteries, reducing the current and / or voltage required to charge and / or fully charge deep cycle batteries, inhibiting acid stratification, reducing internal electrical resistance, inhibiting antimony poisoning, increasing wettability, reducing electrolyte wet-out time, reducing the time required for battery formation due to reduced wet-out time, improving acid diffusion, improving the uniformity of lead-acid batteries, and / or improving cycling performance. According to at least certain embodiments, the disclosure or invention relates to improved separators, where the novel separators include reduced electrical resistance, performance-enhancing additives or coatings, improved fillers, increased wettability, increased acid diffusion, etc.

[0009] To achieve these and other objectives, in certain select embodiments, a separator having a microporous membrane and an optional fibrous mat (laminated or otherwise adjacent to the microporous membrane) is proposed for use in a lead-acid battery, such as an EFB or deep cycle battery, having a negative electrode and a positive electrode with the separator disposed therebetween. Either or both of the microporous membrane or the fibrous mat may comprise natural and / or synthetic rubber and at least one performance-enhancing additive impregnated or coated on at least a portion of either surface of either the microporous membrane or the fibrous mat.

[0010] In accordance with at least certain selected embodiments, a microporous separator is provided that has high (water or acid) wettability. The novel separator with high wettability provides increased accessibility to electrolyte ionic species, thereby facilitating their passage through the separator and reducing electrical resistance.

[0011] In some cases, improved batteries with improved separators containing one or more performance-enhancing additives and / or one or more performance-enhancing coatings may exhibit a 20% reduction in float current, in some cases a 30% reduction, in some cases a 40% reduction in float current, and in some cases more than a 50% reduction, after three weeks of continuous overcharge compared to conventional rubber separators. Batteries with improved separators preserve and maintain the balance of other key desirable mechanical properties of lead-acid battery separators. Such improved separators may also exhibit a much more uniform float current after overcharge compared to conventional separators.

[0012] According to at least one embodiment, a microporous separator is provided that includes one or more performance-enhancing additives and / or coatings, such as one or more surfactants, that can act to inhibit antimony poisoning, reduce water consumption, reduce electrical resistance, and / or improve cycling performance.

[0013] According to certain embodiments, the improved separator can have ribs, protrusions, bumps, embossments, textured features, channels, serrated ribs, battlement ribs, or combinations thereof, on one or both sides of the separator. The separator profile can inhibit acid stratification, thereby improving battery performance and consistency. In some embodiments, the rib pattern used can be a rib pattern similar to that used in golf cart batteries or other deep-cycle batteries. In certain embodiments, the ribs can be of various heights, such as 0.2 mm to 2 mm or more, in some cases greater than 1 mm, in some cases about 1.5 mm, etc., and in certain embodiments, can be spaced apart by various distances, such as 0.2 mm to 10 mm or more, in some cases about 1 to 10 mm, e.g., about 3.5 to 7 mm. In some embodiments, longitudinal or mini-ribs or cross ribs or mini-ribs are included on a surface other than the surface on which the main longitudinal ribs are included, and in some cases such cross ribs are negative cross ribs (preferably negative cross mini-ribs) and / or extend in a direction perpendicular to the direction in which the main longitudinal ribs extend on another surface or face.

[0014] The lead-acid battery separator described herein may comprise a polyolefin microporous membrane further comprising natural or synthetic latex and / or rubber. In preferred embodiments, the latex and / or rubber is uncured. Potentially preferred polyolefin microporous membranes include a polymer, such as polyethylene, e.g., ultra-high molecular weight polyethylene, latex and / or rubber, a particulate filler, and in some embodiments, a residual processing plasticizer (e.g., processing oil), and one or more performance-enhancing additives and / or coatings (e.g., surfactants), and optionally one or more additional additives or agents. The polyolefin microporous membrane may include the particulate filler in an amount of 40% or more by weight of the membrane.

[0015] Selected embodiments of the present invention provide a battery separator having a porous membrane composed of a substrate, a rubber, and at least one performance-enhancing additive. The substrate may be one or more of a polymer, polyolefin, polyethylene, polypropylene, ultra-high molecular weight polyethylene ("UHMWPE"), phenolic resin, polyvinyl chloride ("PVC"), rubber, synthetic wood pulp ("SWP"), lignin, glass fiber, synthetic fiber, cellulosic fiber, and combinations thereof. The rubber may be crosslinked rubber, non-crosslinked rubber, natural rubber, latex, synthetic rubber, and combinations thereof. The rubber may further be methyl rubber, polybutadiene, one or more of chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylic rubber, fluororubber, silicone rubber, copolymer rubber, and any combinations thereof. The copolymer rubber may be styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), ethylene / vinyl acetate rubber, and combinations thereof.

[0016] One aspect of the present invention can provide rubber coated on at least a portion of the surface of a porous membrane or rubber impregnated into at least a portion of a porous membrane. Another aspect of the present invention can provide rubber mixed with a substrate used to form the porous membrane. In a refinement of the exemplary embodiment, the rubber in the substrate is at least about 1% by weight and not more than about 50% by weight. In a further refinement of the exemplary embodiment, the rubber in the substrate is at least about 1% by weight and not more than about 20% by weight.

[0017] In accordance with another aspect of the present invention, the at least one performance enhancing additive is a surfactant, and the surfactant may be any one of a nonionic surfactant, an ionic surfactant, an anionic surfactant, a cationic surfactant, and combinations thereof. According to a refinement of the exemplary embodiment, the at least one performance enhancing additive is present in an amount of at least about 0.5 g / m 2 to about 25g / m 2According to a further refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 20 g / m 2 According to another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 15g / m 2 According to yet another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 10 g / m 2 According to yet another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 6 g / m 2 According to another aspect of the exemplary embodiment, the at least one performance enhancing additive may be a surfactant, a wetting agent, a colorant, an antistatic additive, an antimony suppression additive, a UV protection additive, an antioxidant, or the like, and combinations thereof.

[0018] According to another aspect of the present invention, the substrate comprises any one of silica, dry finely divided silica, precipitated silica, amorphous silica, alumina, talc, fish meal, fish bone meal, and combinations thereof. According to another aspect of the present invention, the substrate comprises a processing plasticizer. The processing plasticizer may be any one of processing oil, petroleum, paraffinic mineral oil, mineral oil, and combinations thereof.

[0019] A refinement of an exemplary embodiment provides a battery separator comprising a mat, such as a fibrous mat, which may include any one of glass fibers, synthetic fibers, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof.

[0020] Another refinement of the exemplary embodiment provides a porous membrane having a backweb thickness of at least about 50 μm to about 500 μm. A further refinement of the exemplary embodiment provides a porous membrane having a backweb thickness of at least about 50 μm to about 350 μm.

[0021] Yet another refinement of the exemplary embodiment provides a porous membrane with ribs, which may be solid ribs, serrated ribs, angled ribs, broken ribs, cross ribs, positive ribs, negative ribs, negative cross ribs, channels, embossments, protrusions, bumps, and combinations thereof. The ribs may also be made of rubber. Exemplary separators may be in various shapes or configurations, such as cut pieces, pockets, sleeves, wraps, envelopes, and hybrid envelopes.

[0022] Another aspect of the present invention provides a lead-acid battery having a positive electrode, a negative electrode adjacent to the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte substantially submerging at least a portion of the positive electrode, at least a portion of the negative electrode, and at least a portion of the separator. An exemplary separator may have a porous membrane comprised of a substrate, at least one performance-enhancing additive, and a rubber. The exemplary lead-acid battery may exhibit reduced water loss, reduced antimony poisoning, increased wettability, faster recharge, improved oxidation stability, reduced float current, reduced end-of-charge current, reduced recharge voltage, and combinations thereof. Exemplary lead-acid batteries may have many applications, such as flat plate batteries, flooded lead-acid batteries, reinforced flooded lead-acid batteries, deep cycle batteries, gel batteries, absorbed glass mat ("AGM") batteries, tubular batteries, inverter batteries, vehicle batteries, starting-lighting-ignition ("SLI") batteries, idle-start-stop ("ISS") batteries, car batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid vehicle batteries, electric vehicle batteries, e-rickshaw batteries, or e-bike batteries. Exemplary lead-acid batteries can operate in a partial state of charge, while running, while stationary, in backup power applications, cycling applications, or combinations thereof.

[0023] An exemplary lead-acid battery may further include a mat adjacent to at least one of the positive electrode, the negative electrode, or the separator. An exemplary mat may be a fibrous mat and may be composed of glass fibers, synthetic fibers, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof.

[0024] Yet another aspect of the present invention provides a method for manufacturing an exemplary separator by combining a mixture of one or more substrates, a rubber, and at least one additive and extruding the mixture into a membrane. Yet another aspect of the present invention provides a method for manufacturing an exemplary separator by combining a mixture of a polymer and at least one additive, extruding the mixture into a membrane, and adding the rubber to the membrane. Exemplary methods can add the rubber to the membrane by laminating the rubber to at least a portion of the membrane, impregnating the rubber to at least a portion of the membrane, coating the rubber slurry on at least a portion of the membrane, immersing at least a portion of the membrane in the rubber slurry, or forming rubber ribs on the membrane.

[0025] Another select embodiment of the present invention provides another method of manufacturing an exemplary separator by combining a mixture of one or more substrates with a rubber, extruding the mixture into a film, and adding at least one additive to the film. At least one additive can be added to the membrane by laminating at least a portion of the membrane, impregnating at least a portion of the membrane with at least one additive, coating at least a portion of the membrane with at least one additive, or soaking the membrane in at least one additive.

[0026] Yet another select embodiment of the present invention provides a method of manufacturing an exemplary separator by combining a mixture of one or more substrates, extruding the mixture into a film, adding a rubber to the film, and adding at least one additive to the film.

[0027] In certain preferred embodiments, the present disclosure or invention provides a flexible battery separator that unexpectedly addresses an unmet need in the deep cycle battery industry through a synergistic combination of components and physical properties and characteristics, resulting in an improved battery separator (a separator having a microporous membrane comprised of a polyolefin, such as polyethylene, and a quantity of rubber and / or latex) that meets or, in certain embodiments, exceeds the performance of previously known flexible separators made entirely of rubber currently used in many deep cycle battery applications, such as golf cart (golf car) and / or e-rickshaw battery applications. In particular, the inventive separators described herein are more robust, less brittle, less brittle, more stable over time, and less expensive than the pure cross-linked latex and / or rubber separators traditionally used in deep cycle batteries, such as golf cart batteries. Flexible separators containing the performance-enhancing additives of the present invention combine the desirable robust physical and mechanical properties of polyethylene-based separators with the Sb suppression capabilities of conventional separators made entirely from crosslinked latex and / or rubber, while improving the end-of-charge current and end-of-charge potential of battery systems using the separators. [Brief explanation of the drawings]

[0028] [Figure 1] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 2A] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 2B] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 2C] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 2D] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 2E] 1 shows a general physical depiction of an exemplary separator of the present invention. [Figure 3A]1 includes linear sweep cyclic voltammetry curves for the first four cycles of a battery tested with a separator according to Example 1. [Figure 3B] 1 includes linear sweep cyclic voltammetry curves for the first four cycles of a battery tested with a separator according to Control 1. [Figure 4A] 1 includes linear sweep cyclic voltammetry curves for the first four cycles of a battery tested with a separator according to Example 1 after spiking the electrolyte with the addition of antimony. [Figure 4B] 1 includes linear sweep cyclic voltammetry curves for the first four cycles of a battery tested with a separator according to Control 1 after spiking the electrolyte with the addition of antimony. [Figure 5] 4C is a graph comparing various cycle 4 results obtained from testing separators according to Example 1 and Control 1 and FIGS. 3A-4B. DETAILED DESCRIPTION OF THE INVENTION

[0029] physical properties 1, an exemplary separator 100 has a top edge 101, a bottom edge 103, side edges 105a, 105b, and a machine direction ("MD") and a cross-machine direction ("CMD"). The exemplary separator includes a backwall of a porous or microporous membrane. The separator may comprise a series of primary or positive ribs 102 extending from the backweb 102 and preferably aligned along the machine direction, or MD, of the separator. As shown, the ribs 104 are sawtooth. However, the ribs 104 may also be solid ribs, grooves, textured areas, serrated or sawtooth ribs, solid ribs, battlements or battlement ribs, broken ribs, angled ribs, straight ribs, curved or sinusoidal ribs, zigzag ribs, embossments, dimples, or the like, extending from or into the backweb 102. In some embodiments, the positive ribs may be at an angle greater than 0° and less than 180°, or greater than 180° and less than 360°, and the negative cross ribs may be aligned on the second surface of the porous membrane generally parallel to the separator's top edge, or CMD.

[0030] Although the exemplary embodiment places separator 100 in a battery (not shown) with ribs 104 facing the positive electrode (not shown), this is not required. Ribs 104 may be referred to as positive-side ribs when they face the positive electrode. Ribs (not shown) extending from the opposite side of the microporous membrane may face the negative electrode (not shown) and be arranged in the longitudinal direction (MD) or transverse direction (CMD). When arranged along the CMD, they are generally referred to as "cross ribs," and as described below, are referred to as "negative-side cross ribs" or "NCR." Separator 100 is typically placed in a battery to position the negative-side cross ribs toward the negative electrode, although this is not required. Furthermore, in relation to the positive-side ribs, the negative-side ribs may be the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs, NCR, diagonal ribs, or a combination thereof. Furthermore, the negative and / or positive electrode surfaces of the separator may be entirely or partially rib-free, and one or both sides of the separator may be smooth or flat.

[0031] Referring now to Figures 2A through 2E, several embodiments of ribbed separators with different rib geometries are shown. The ribs shown may be preferred on the positive electrode side. The angled rib pattern in Figures 2A through 2C may be a preferred Daramic® RipTide® acid-mixed rib geometry, which may help reduce or eliminate acid stratification in certain batteries. The geometry in Figure 2D may be a longitudinal sawtooth rib pattern. The geometry in Figure 2E may be a diagonal offset rib pattern. The negative electrode side may have no ribs (smooth), the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs or NCR, diagonal ribs, or a combination thereof.

[0032] Manufacturing / Thickness In some embodiments, the porous separator membrane can have a backweb thickness of about 50 μm to 1.0 mm, at least about 50 μm, at least about 75 μm, at least about 100 μm, at least about 125 μm, at least about 150 μm, at least about 175 μm, at least about 200 μm, at least about 225 μm, at least about 250 μm, at least about 275 μm, at least about 300 μm, at least about 325 μm, at least about 350 μm, at least about 375 μm, at least about 400 μm, at least about 425 μm, at least about 450 μm, at least about 475 μm, or at least about 500 μm (although certain embodiments provide very thin, flat backweb thicknesses, e.g., 10 μm to 50 μm thick). In certain embodiments, the backweb thickness can be about 125 μm ± 35 μm or less.

[0033] rib The ribs may be continuous, discontinuous, solid, porous, or non-porous on the positive, negative, or both sides, and may be mini-ribs or cross mini-ribs on the negative side. The ribs may be serrated in certain preferred embodiments (e.g., serrated positive-side ribs, negative-side ribs, or both). The serrated or serrated ribs may have an average tip length of about 0.05 mm to about 1 mm. For example, the average tip length may be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, or 1.5 mm. , 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0034] The serrations or saw-tooth ribs may have an average baseline length of about 0.05 mm to about 1 mm. For example, the average baseline length may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm, and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0035] When present, serrations or sawtooth ribs may have an average height of about 0.05 mm to about 4 mm. For example, the average height may be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less. In embodiments in which the height of the serrations is the same as the height of the ribs, the sawtooth ribs may also be referred to as protrusions. Such ranges may apply to separators for industrial traction start / stop batteries, where the overall separator thickness may typically be about 1 mm to about 4 mm, and to separators for automotive start / stop batteries, where the overall separator thickness may be slightly smaller (e.g., typically about 0.3 mm to about 1 mm).

[0036] The serrations or sawtooth ribs may have an average center-to-center pitch within a column in the machine direction of about 0.1 mm to about 50 mm. For example, the average center-to-center pitch may be greater than or equal to about 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm, and / or less than or equal to about 1.5 mm, 1.25 mm, 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm. Additionally, adjacent columns of serrations or sawtooth ribs may be similarly positioned in the same machine direction or offset. In an offset configuration, adjacent serrations or sawtooth ribs are positioned at different machine direction positions. FIG. 1A shows sawtooth ribs positioned in an offset configuration.

[0037] The serrations or saw-tooth ribs may have an average height-to-base width ratio of about 0.1:1 to about 500:1. For example, the average height-to-base width ratio may be greater than or equal to about 0.1:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, or 450:1, and / or less than or equal to about 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, or 25:1.

[0038] The serrations or saw-tooth ribs may have an average base width to tip width ratio of about 1000:1 to about 0.1:1. For example, the average base width to tip width ratio may be about 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 or more, and / or or may be less than about 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1.

[0039] In some embodiments, the separator can feature a combination of solid ribs, serrations or sawtooth ribs, dimples, or any combination thereof. For example, the separator can have a series of sawtooth ribs extending from top to bottom along the separator and a second series of sawtooth ribs extending horizontally along the separator. In other embodiments, the separator can have alternating solid ribs, sawtooth ribs, dimples, continuous ribs, interrupted ribs, broken solid ribs, or any combination thereof.

[0040] In some selected embodiments, the porous separator may have longitudinal or cross ribs on the negative electrode side as protrusions on the surface opposite the membrane. The negative electrode side, or backside, ribs may be parallel to the top edge of the separator or may be disposed at an angle thereto. For example, the cross ribs may be oriented at approximately 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15°, or 5° relative to the top edge. The cross ribs may be oriented at approximately 90 to 60°, 60 to 30°, 60 to 45°, 45 to 30°, or 30 to 0° relative to the top edge. Typically, the cross ribs are present on the surface of the membrane facing the negative electrode. In some embodiments of the invention, the ribbed membrane may have a transverse cross rib height HNCR of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the invention, the ribbed membrane may have a transverse cross rib height of no more than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0041] In some embodiments of the invention, the ribbed membrane may have a transverse cross rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the invention, the ribbed membrane may have a transverse cross rib width of no more than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0042] In certain selected embodiments, the porous membrane may have a transverse cross rib height of about 0.10 to 0.15 mm and a longitudinal rib height of about 0.10 to 0.15 mm. In some embodiments, the porous membrane may have a transverse cross rib height of about 0.10 to 0.125 mm and a longitudinal rib height of about 0.10 to 0.125 mm.

[0043] Such negative cross ribs may be smaller and closer together than the positive ribs. The positive ribs 104 may have a height of 8 μm to 1 mm and be spaced apart by 1 μm to 20 mm, while the preferred backweb thickness of the microporous polyolefin membrane (not including ribs or embossments) may be about 50 μm to about 500 μm (e.g., in certain embodiments, about 125 μm or less). For example, the ribs may be spaced apart by 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, and similar increments up to a maximum of 20 mm.

[0044] The negative electrode cross ribs may have a height of about 25 μm to about 100 μm, preferably about 50 μm to 75 μm, but may be as low as 25 μm. In some cases, the NCR may be about 25 μm to about 250 μm, preferably about 50 μm to 125 μm, or preferably about 50 μm to 75 μm.

[0045] Thickness In certain select embodiments, exemplary microporous membranes have a thickness of at least 0.1 mm, 0.2 mm, The microporous membrane may have a backweb thickness of about 0.1 to 1.0 mm, 0.1 to 0.8 mm, 0.1 to 0.5 mm, 0.1 to 0.5 mm, 0.1 to 0.4 mm, or 0.1 to 0.3 mm. In some embodiments, the microporous membrane may have a backweb thickness of about 0.2 mm or 200 μm.

[0046] (Hybrid) Envelope / Shape The separator 100 can be provided as a flat plate, one or more leaves, a wrap, a sleeve, or as an envelope or pocket separator. An exemplary envelope separator can encase a positive electrode (a "positive electrode-encasing separator"), resulting in the separator having two inner surfaces facing the positive electrode and two outer surfaces facing the adjacent negative electrode. Alternatively, another exemplary envelope separator can encase a negative electrode (a "negative electrode-encasing separator"), resulting in the separator having two inner surfaces facing the negative electrode and two outer surfaces facing the adjacent positive electrode. In such an envelope separator, the bottom edge 103 can be a folded or sealed crease edge. Additionally, the side edges 105a, 105b can be continuously or intermittently sealed seam edges. The edges can be bonded or sealed by adhesive, heat, ultrasonic welding, etc., or any combination thereof.

[0047] Certain exemplary separators can be processed to form hybrid envelopes. Hybrid envelopes can be provided by folding a separator sheet in half to form the envelope and forming one or more cuts or openings before, during, or after bonding the edges of the separator sheet together. The length of the openings can be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the overall edge length. The length of the openings can be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the overall edge length. Hybrid envelopes can have 1 to 5, 1 to 4, 2 to 4, 2 to 3, or 2 openings, which may or may not be evenly spaced along the length of the lower edge. The corners of the envelope are preferably free of openings. The cuts may be cut after the separator is folded and sealed to create the envelope, or the cuts may be formed prior to forming the porous membrane into the envelope.

[0048] Some other exemplary embodiments of separator assembly structures include positive-facing ribs 104, negative-facing ribs 104, negative or positive electrode envelopes, negative or positive electrode sleeves, negative or positive electrode hybrid envelopes, both electrodes that may be wrapped or sleeved, and any combination thereof.

[0049] composition In certain embodiments, the improved separator may comprise a porous membrane that may be made from a natural or synthetic substrate, processing plasticizers, fillers, natural or synthetic rubber or latex, and one or more other additives and / or coatings, and the like.

[0050] Base material In certain embodiments, exemplary natural or synthetic substrates may include polymers, thermoplastic polymers, phenolic resins, natural or synthetic rubbers, synthetic wood pulp, lignin, glass fibers, synthetic fibers, cellulosic fibers, and any combination thereof. In certain preferred embodiments, exemplary separators are microporous membranes made of thermoplastic polymers. Exemplary thermoplastic polymers can include, in principle, any acid-resistant thermoplastic material suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers can include polyvinyls and polyolefins. In certain embodiments, polyvinyls can include, for example, polyvinyl chloride ("PVC"). In certain preferred embodiments, polyolefins can include, for example, polyethylene, polypropylene, ethylene butene copolymers, and any combination thereof, but preferably include polyethylene. In certain embodiments, exemplary natural or synthetic rubbers can include, for example, latex, non-crosslinked or crosslinked rubber, crumb or gland rubber, and any combination thereof.

[0051] Polyolefin In certain embodiments, the porous membrane layer preferably comprises a polyolefin, particularly polyethylene. Preferably, the polyethylene is high molecular weight polyethylene ("HMWPE") (e.g., polyethylene having a molecular weight of at least 600,000). Even more preferably, the polyethylene is an ultra-high molecular weight polyethylene (“UHMWPE”) (e.g., a polyethylene having a molecular weight of at least 1,000,000, particularly greater than 4,000,000, and most preferably 5,000,000 to 8,000,000, as measured by viscometry and calculated according to the Margolies equation), a standard load melt index of essentially zero (0) (measured as specified in ASTM D1238 (condition E) using a standard load of 2,160 g), and a viscosity number of 600 ml / g or greater, preferably 1,000 ml / g or greater, more preferably 2,000 ml / g or greater, and most preferably 3,000 ml / g or greater (determined on a solution of 0.02 g of polyolefin in 100 g of decalin at 130° C.).

[0052] rubber The novel separators disclosed herein may comprise latex and / or rubber. Rubber, as used herein, refers to rubber, latex, natural rubber, synthetic rubber, crosslinked or uncrosslinked rubber, cured or uncured rubber, crumb or ground rubber, or mixtures thereof. Exemplary natural rubbers may include one or more polyisoprene blends commercially available from various suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylic rubber, fluororubber, silicone rubber, and copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber ("EPM" and "EPDM"), and ethylene / vinyl acetate rubber. The rubber may be crosslinked or uncrosslinked; in certain preferred embodiments, the rubber is uncrosslinked. In certain embodiments, the rubber may be a mixture of crosslinked and uncrosslinked rubber.

[0053] plasticizer In certain embodiments, exemplary processing plasticizers may include processing oils, petroleum oils, paraffinic mineral oils, mineral oils, and any combination thereof.

[0054] Filler In certain embodiments, exemplary fillers may include dry, finely divided silica, precipitated silica, amorphous silica, alumina, talc, fish meal, fish bone meal, and the like, and any combination thereof. In certain preferred embodiments, the filler is one or more silicas. Silica, which has a relatively high oil absorption and affinity for plasticizers (e.g., mineral oil), is desirable so that it can be dispersed in a mixture of polyolefin substrate (e.g., polyethylene) and mineral oil when forming lead-acid battery separators of the type described herein. In some selected embodiments, the filler has a particle size of 25 μm or less, and in some instances 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm. The average particle size of the silica filler particles is as follows: In some examples, the average particle size of the silica filler particles is 15 to 25 μm. The particle size of the silica filler and / or the surface area of ​​the silica filler are related to the oil absorption capacity. The silica particles in the final product, i.e., separator, can fall within the above particle size range. However, the initial silica used as a raw material may occur as one or more clumps and / or agglomerates and have a size of about 200 μm or larger. In some embodiments, the final separator sheet has a residual or final oil content ranging from about 0.5% to about 40%, in some embodiments from about 10% to about 30% residual processing oil, and in some examples from about 20% to about 30% residual processing oil or residual oil, by weight of the separator sheet product. With regard to the pore size of the separator membrane, the pore size may be submicron to 100 μm, and in certain embodiments, from about 0.1 μm to about 10 μm. The porosity of the separator membranes described herein may be greater than 50% in certain embodiments.

[0055] The filler can further reduce the total electrical resistance or ER of the battery, such as an enhanced flooded battery or system, by suppressing the so-called hydration layer of electrolyte ions and facilitating their permeation through the membrane.

[0056] The one or more fillers may include various species (e.g., polar species such as metals) that promote the flow of electrolytes and ions through the separator, which also reduces the overall electrical resistance when such separators are used in flooded batteries, such as enhanced flooded batteries.

[0057] Additives / Surfactants In certain embodiments, exemplary separators may include one or more performance-enhancing additives added to the separator, i.e., microporous membrane. The performance-enhancing additives may be surfactants, wetting agents, colorants, antistatic additives, antimony suppression additives, UV protection additives, antioxidants, and the like, and any combination thereof. In certain embodiments, the added surfactant may be an ionic, cationic, anionic, or nonionic surfactant.

[0058] In certain embodiments described herein, small amounts of anionic or nonionic surfactants are added to the microporous membranes or separators of the present invention. Because of the low amount of surfactant, desirable characteristics can include lower total organic carbon ("TOC") and / or lower volatile organic compounds ("VOCs").

[0059] Certain suitable surfactants are nonionic, while other suitable surfactants are anionic. The additive may be a single surfactant or a mixture of two or more surfactants, such as two or more anionic surfactants, two or more nonionic surfactants, or at least one ionic surfactant and at least one nonionic surfactant. The selected suitable surfactant may have an HLB value of less than 6, preferably less than 3. The use of these certain suitable surfactants in conjunction with the separators of the present invention described herein can result in improved separators that, when used in lead-acid batteries, result in reduced water loss, reduced antimony poisoning, improved cycling, reduced float current, reduced float potential, or the like, or any combination thereof, in the lead-acid batteries. Suitable surfactants include surfactants such as alkyl sulfates, alkylaryl sulfonates, alkylphenol-alkylene oxide adducts, soaps, alkylnaphthalene sulfonates, one or more sulfosuccinates such as anionic sulfosuccinates, dialkyl esters of sulfosuccinates, amino compounds (primary, secondary, tertiary, or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, and salts of mono- and di-alkyl phosphate esters. Additives include polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and mixtures thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicones, and the like. The surfactants may include non-ionic surfactants such as ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters and sucrose fatty acid esters.

[0060] In certain embodiments, the additive can be represented by a compound of formula (I).

number

[0061] The ratio of oxygen atoms to carbon atoms in the compounds according to formula (I) ranges from 1:1.5 to 1:30, and m and n cannot simultaneously be 0, although preferably only one of the variables n and m is not 0.

[0062] By non-aromatic hydrocarbon group is meant a group that does not contain or represent an aromatic group. The hydrocarbon group may be interrupted by oxygen atoms (i.e., contains one or more ether groups).

[0063] R is preferably a linear or branched aliphatic hydrocarbon group which may be interrupted by an oxygen atom. Saturated, non-bridged hydrocarbon groups are very particularly preferred. However, as noted above, R may in certain embodiments contain an aromatic ring.

[0064] By using the compound of formula (I) in the preparation of a battery separator, the separator can be effectively protected from oxidative breakdown.

[0065] Preferred is a battery separator containing a compound according to formula (I), wherein: R is a hydrocarbon radical having 10 to 180, preferably 12 to 75 and very particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20 and very particularly preferably 1 to 8 oxygen atoms, particularly preferably a hydrocarbon radical of the formula R 2 -[(OC2H4)p(OC3H6) q ]-, where: R 2 is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 carbon atoms, and R 2 may be linear or non-linear, such as containing an aromatic ring. P is an integer of from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4. q is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4. Compounds in which the sum of p and q is 0 to 10, especially 0 to 4, are particularly preferred. n=1. m=0.

[0066] formula R 2 -[(OC2H4) p (OC3H6) q ]- should be understood to include these compounds, but in which the sequence of the groups in the brackets differs from that shown. For example, compounds in which the groups in the brackets are formed by substituting (OC2H4) and (OC3H6) groups are also suitable according to the present invention.

[0067] R 2 Additives in which OC2H4 preferably represents OCH2CH2 and OC3H6 represents OCH(CH3)2 and / or OCH2CH2CH3 have proven particularly advantageous.

[0068] As a preferred additive, mention may be made in particular of alcohols (p=q=0, m=0). Primary alcohols are particularly preferred, and fatty alcohol ethoxylates (p=1 to 4, q=0), fatty alcohol propoxylates (p=0, q=1 to 4) and fatty alcohol alkoxylates (p=1 to 2, q=1 to 4) are preferred. Fatty alcohol alkoxylates are available, for example, by reacting the corresponding alcohol with ethylene oxide or propylene oxide.

[0069] Additives of the type m=0 which are insoluble or only sparingly soluble in water and sulfuric acid have proven to be particularly advantageous.

[0070] Also preferred is an additive comprising a compound according to formula (I), wherein: R is an alkane radical having from 20 to 4200, preferably from 50 to 750 and very particularly preferably from 80 to 225 carbon atoms. M is an alkali metal or alkaline earth metal ion, H + or NH4 + , especially Li + , Na + and K. + or H + and other alkali metal ions, where all variables M are simultaneously H + does not have the meaning of n=0. m is an integer from 10 to 1400. x=1 or 2.

[0071] Salt additives In certain embodiments, suitable additives may include, in particular, polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers, whose acid groups are at least partially neutralized, i.e., preferably 40%, particularly preferably 80%. The percentage refers to the number of acid groups. Polyacrylic acid (polymethacrylic acid) present entirely in salt form is very particularly preferred. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium (NR4, where R is a hydrogen or carbon functional group). Polyacrylic acid (polymethacrylic acid) may include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers. Polyacrylic acid (polymethacrylic acid), in particular, has an average molar mass M of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, and very particularly preferably 1,000 to 4,000 g / mol. w The molecular weight of polyacrylic acid (polymethacrylic acid) polymers and copolymers is determined by measuring the viscosity of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution (Fikentscher's constant).

[0072] Copolymers of (meth)acrylic acid are also suitable, especially those containing, in addition to (meth)acrylic acid, ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and / or ethylhexyl acrylate as comonomers. Preference is given to copolymers containing at least 40% by weight, preferably at least 80% by weight, of (meth)acrylic acid monomer, the proportions being based on the acid form of the monomer or polymer.

[0073] For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide and especially sodium hydroxide are particularly suitable. Also, coatings and / or additives for reinforcing the separator include, for example, metal alkoxylates. By way of example only (and not intended to be limiting), the metal may be Zn, Na, or Al, by way of example only, sodium ethoxide.

[0074] In some embodiments, the microporous polyolefin membrane may include a coating on one or both sides of such layer. Such coatings may include surfactants or other materials. In some embodiments, the coating may include one or more materials described, for example, in U.S. Patent Publication No. 2012 / 0094183, which is incorporated herein by reference. Such coatings can reduce grid corrosion, extend battery life, and prevent dryout and / or water loss, for example, by reducing the overcharge voltage of the battery system.

[0075] ratio In certain selected embodiments, the membrane may be made by combining about 5 to 15 wt% polymer, in some cases about 10 wt% polymer (e.g., polyethylene), about 10 to 75 wt% filler (e.g., silica), in some cases about 30 wt% filler, and about 10 to 85 wt% processing oil, in some cases about 60 wt% processing oil. In other embodiments, the filler content is reduced and the oil content is high, e.g., greater than about 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, or 70 wt%. The filler to polymer (by weight) ratio may be, for example, about 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1, or 6:1 (or may be within approximately these specified ranges). The filler to polymer ratio (by weight) can be from about 1.5:1 to about 6:1, in some cases from 2:1 to 6:1, from about 2:1 to 5:1, from about 2:1 to 4:1, and in some cases from about 2:1 to about 3:1. The amounts of filler, oil, and polymer are all balanced for feasibility and desired separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, torsion, etc.

[0076] According to at least one embodiment, the porous membrane can include UHMWPE mixed with processing oil and precipitated silica. According to at least one embodiment, the microporous membrane can include UHMWPE mixed with processing oil, additives, and precipitated silica. The mixture can also include small amounts of other additives or agents common in separator technology (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, etc., and any combination thereof). In some examples, the microporous polymer layer can be a homogeneous mixture of 8 to 100% by volume polyolefin, 0 to 40% by volume plasticizer, and 0 to 92% by volume inert filler. A preferred plasticizer is petroleum. Plasticizers are useful for imparting porosity to battery separators because they are the component most easily removed from polymer-filler-plasticizer compositions by solvent extraction and solvent drying.

[0077] In certain embodiments, the microporous membranes disclosed herein may comprise latex and / or rubber, which may be natural rubber, synthetic rubber, or a mixture thereof. Natural rubber may include one or more polyisoprene blends commercially available from various suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylic rubber, fluororubber, silicone rubber, and copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber may be crosslinked or non-crosslinked, and in certain preferred embodiments, the rubber is non-crosslinked. In certain embodiments, the rubber may be a mixture of crosslinked and non-crosslinked rubber. The rubber should comprise at least about 1 wt.% of the final separator weight (the weight of the polyolefin separator sheet or layer containing the rubber and / or latex). , 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%. In certain embodiments, the rubber may be present in an amount of about 1 to 20 wt%, 2 to 20 wt%, 2.5 to 15 wt%, 2.5 to 12.5 wt%, 2.5 to 10 wt%, or 5 to 10 wt%. The microporous membrane may even have a rubber and / or latex content as high as 50 wt%. The amounts of rubber, filler, oil, and polymer are all balanced for feasibility and desired separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, torsion, etc.

[0078] Microporous membranes made according to the present invention, including polyethylene and a filler (e.g., silica), typically have a residual oil content; in some embodiments, such residual oil content is about 0.5% up to about 40% of the total weight of the separator membrane (in some cases, about 10 to 40% of the total weight of the separator membrane, and in some cases, about 20 to 40% of the total weight). In certain selected embodiments herein, some or all of the residual oil in the separator membrane may be replaced by adding a large amount of a performance-enhancing additive, such as a surfactant, a surfactant with a hydrophilic-lipophilic balance ("HLB") less than 6, or a nonionic surfactant. For example, the performance-enhancing additive, such as a surfactant or nonionic surfactant, may account for up to 0.5% of the total amount of residual oil (e.g., 20%, 30%, or even 40%) of the total weight of the microporous separator membrane, thereby partially or completely replacing the residual oil in the separator membrane.

[0079] manufacturing In some embodiments, exemplary porous membranes may be made by mixing the components in an extruder. For example, about 30% by weight of silica may be mixed with about 10% by weight of UHMWPE and about 60% processing oil in an extruder. Exemplary microporous membranes may be made by passing the components through a heated extruder, and then forcing the extrudate produced by the extruder through a die and into a nip formed by two heated press or calender stacks or rolls to form a continuous web. A solvent can be used to extract a substantial amount of the processing oil from the web. The web can then be dried, slit into lanes of a predetermined width, and wound onto a roll. Alternatively or additionally, the press or calender roll can be engraved with various groove patterns to impart ribs, grooves, textured areas, serrations, sawtooth ribs, battlements or battlement ribs, broken ribs, angled ribs, straight ribs, curved or sinusoidal ribs, embossments, dimples, or any combination thereof, extending to or from the microporous membrane to form a separator.

[0080] Rubber manufacturing In some embodiments, exemplary porous membranes may be made by mixing components in an extruder. For example, about 5 to 15 wt. % polymer (e.g., polyethylene), about 10 to 75 wt. % filler (e.g., silica), about 1 to 50 wt. % rubber and / or latex, and about 10 to 85 wt. % processing oil may be mixed in the extruder. Exemplary microporous membranes may be made by passing the components through a heated extruder, forcing the extrudate produced by the extruder through a die and into a nip formed by two heated presses or calender stacks or rolls to form a continuous web. A substantial amount of the processing oil can be extracted from the web using a solvent. The web can then be dried, slit into lanes of a predetermined width, and wound onto a roll. Alternatively or additionally, the press or calender rolls may be engraved with various groove patterns to impart ribs, grooves, textured areas, serrations, sawtooth ribs, battlements or battlement ribs, broken ribs, angled ribs, straight ribs, curved or sinusoidal ribs, embossments, dimples, etc., or any combination thereof (as described above) to the separator. The amounts of rubber, filler, oil, and polymer may all be determined by feasibility and desirability. A balance is maintained for desirable separator properties such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, torsion, and the like.

[0081] In addition to being added to the extruder components, certain embodiments bond the rubber to the microporous membrane after extrusion. For example, the rubber may be coated on one or both sides, preferably the side facing the negative electrode, with a liquid slurry containing rubber and / or latex, optionally silica, and water, and then dried so that a film of this material forms on the surface of the exemplary microporous membrane. To improve the wettability of this layer, known wetting agents can be added to the slurry used in lead-acid batteries. In certain embodiments, the slurry can also contain one or more performance-enhancing additives described herein. A porous layer and / or film is formed on the surface of the separator that adheres very tightly to the microporous membrane and increases electrical resistance only slightly, if at all. After the rubber is added, it may be further compressed using a mechanical press or a calender stack or roll. Another possible method for applying the rubber and / or latex is to apply the rubber and / or latex slurry to one or more surfaces of the separator by dip coating, roller coating, spray coating, curtain coating, or any combination thereof. These processes may occur before or after the processed oil is extracted, or before or after it is slit and laned.

[0082] A further embodiment of the present invention involves attaching the rubber to the membrane by impregnation and drying.

[0083] Surfactant-based manufacturing In certain embodiments, optional additives or agents (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, etc., and any combination thereof) may also be mixed with other components in the extruder. Microporous membranes according to the present disclosure can then be extruded into sheets or webs and finished in substantially the same manner as described above.

[0084] In certain embodiments, one or more additives can be applied to the separator porous membrane as it is completed (e.g., after a large amount of processing oil has been extracted, or before or after the introduction of rubber), in addition to or instead of being added in the extruder. According to certain preferred embodiments, the additive or a solution of the additive (e.g., an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for applying thermally unstable additives and additives that are soluble in the solvent used to extract the processing oil. Low-molecular-weight alcohols, such as methanol and ethanol, and mixtures of these alcohols with water are particularly suitable as solvents for the additives of the present invention. Application can be performed on the side facing the negative electrode, the side facing the positive electrode, or on both sides of the separator. Application can also be performed during the extraction of the pore-forming agent (e.g., processing oil) in a solvent bath. In certain select embodiments, a portion of the performance-enhancing additive, such as a surfactant coating or performance-enhancing additive (or both), added to the extruder before the separator is produced can bind with antimony in the battery system, deactivating the antimony, forming compounds with antimony, causing the antimony to sink into the battery's mud pan, and / or preventing antimony from precipitating on the negative electrode. The surfactant or additive can also be added to the electrolyte, glass mat, battery case, pasting paper, pasting mat, etc.

[0085] In certain embodiments, the additive (e.g., a nonionic surfactant, an anionic surfactant, or a mixture thereof) is present in an amount of at least 0.5 g / m 2 , 1.0 g / m 2 , 1.5g / m 2 , 2.0 g / m 2 , 2.5g / m 2 , 3.0 g / m 2 , 3.5g / m 2 , 4.0g / m 2 , 4.5g / m 2 , 5.0g / m 2 , 5.5g / m 2 , 6.0 g / m 2 , 6.5g / m 2 , 7.0 g / m 2 , 7.5g / m2 , 8.0 g / m 2 , 8.5g / m 2 , 9.0 g / m 2 , 9.5g / m 2 or 10.0 g / m 2 , or even up to about 25.0 g / m 2 The additive may be present at a density or add-on level of 0.5 to 15 g / m 2 , 0.5 to 10g / m 2 , 1.0 to 10.0 g / m 2 , 1.5 to 10.0 g / m 2 , 2.0 to 10.0 g / m 2 , 2.5 to 10.0 g / m 2 , 3.0 to 10.0 g / m 2 , 3.5 to 10.0 g / m 2 , 4.0 to 10.0 g / m 2 , 4.5 to 10.0 g / m 2 , 5.0 to 10.0 g / m 2 , 5.5 to 10.0 g / m 2 , 6.0 to 10.0 g / m 2 , 6.5 to 10.0 g / m 2 , 7.0 to 10.0 g / m 2 , 7.5 to 10.0 g / m 2 , 4.5 to 7.5 g / m 2 , 5.0 to 10.5 g / m 2 , 5.0 to 11.0 g / m 2 , 5.0 to 12.0 g / m 2 , 5.0 to 15.0 g / m 2 , 5.0 to 16.0 g / m 2 , 5.0 to 17.0 g / m 2 , 5.0 to 18.0 g / m 2 , 5.0 to 19.0 g / m 2 , 5.0 to 20.0 g / m 2 , 5.0 to 21.0 g / m 2 , 5.0 to 22.0 g / m 2 , 5.0 to 23.0 g / m 2 , 5.0 to 24.0 g / m 2 , or 5.0 to 25.0 g / m 2density or add-on level on the separator.

[0086] Application can also be performed by immersing the battery separator in the additive or a solution of the additive (solvent bath application) and removing the solvent as needed (e.g., by drying). In this way, application of the additive can be combined with extraction, which is often applied, for example, during membrane formation. Other preferred methods are to apply one or more additives to the separator surface by spraying the additive onto the surface, dip coating, roller coating, or curtain coating.

[0087] In certain embodiments described herein, small amounts of ionic, cationic, anionic, or nonionic surfactants are added to the separators of the present invention. In such instances, desirable characteristics include lower amounts of total organic carbon and / or lower amounts of volatile organic compounds (due to the lower amounts of surfactant), which can produce desirable separators of the present invention according to such embodiments.

[0088] Bonding with fibrous mats In certain embodiments, exemplary separators according to the present disclosure can be combined with another layer (laminated or otherwise) such as a fibrous layer or fibrous mat having improved wicking properties and / or improved electrolyte wetting or retention. The fibrous mat can be a woven, nonwoven, fleece, mesh, net, single layer, multiple layers (each layer can have the same, similar, or different properties from the other layers) made from glass or synthetic fibers, a fleece or woven made from synthetic fibers, a blend of glass and synthetic fibers, or paper, or any combination thereof.

[0089] In certain embodiments, the fibrous mat (laminated or otherwise) may be used as a carrier for additional materials. The additional materials may include, for example, rubber and / or latex, optionally silica, water, and / or one or more performance-enhancing additives, such as various additives described herein, or any combination thereof. By way of example, the additional materials may be provided in the form of a slurry that can then be coated onto one or more surfaces of the fibrous mat to form a film or that can penetrate and impregnate the fibrous mat.

[0090] When a fibrous layer is present, the microporous membrane preferably has a larger surface area than the fibrous layer. Thus, when the microporous membrane and fibrous layer are bonded together, the fibrous layer does not completely cover the microporous layer. Preferably, at least two opposing edge regions of the membrane layer are left uncovered to provide edges for heat sealing to facilitate optional formation of pockets, envelopes, etc. The thickness of such a fibrous mat may, in some embodiments, be at least 100 μm, at least about 200 μm, at least about 250 μm, at least about 300 μm, at least about 400 μm, at least about 500 μm, at least about 600 μm, at least about 700 μm, at least about 800 μm, at least about 900 μm, at least about 1 mm, at least about 2 mm, etc. The subsequent stacked separator can be cut into small pieces. In certain embodiments, the fibrous mat is laminated to the ribbed surface of the microporous membrane. In certain embodiments, handling and / or assembly advantages are provided to battery manufacturers by the improved separators described herein when supplied in rolls and / or cut pieces. Also, as previously mentioned, the improved separator may be a free-standing separator sheet or layer without one or more fibrous mats or the like attached thereto.

[0091] When laminated to the microporous membrane, the fibrous mat may be adhered by adhesives, heat, ultrasonic welding, compression, or the like, or any combination thereof.

[0092] porosity The separator of the present invention preferably comprises a porous membrane, such as a microporous membrane having pores less than about 5 μm, preferably less than about 1 μm, a mesoporous membrane, or a microporous membrane having pores greater than about 1 μm. In certain preferred embodiments, an exemplary porous membrane is a microporous membrane having a pore size of about 0.1 μm and a porosity of about 60%.

[0093] basic weight In certain selected embodiments, exemplary separators have a porosity of 1000 psi (g / m 2 The separator can be characterized by its basis weight (also called areal weight) measured in units of m². Exemplary separators can exhibit low basis weights. For example, an exemplary separator has a basis weight of 140 g / m². 2 Below 130g / m 2 Below 120g / m 2 Below 110g / m 2 Below 100g / m 2 Below 90g / m 2 An exemplary separator preferably has a weight of about 130 g / m 2 to about 90g / m 2 or less, preferably about 120 g / m 2 to about 90g / m 2 It has the following basis weight:

[0094] Basis weight is determined by simply weighing a sample and dividing that value by the area of ​​the sample. For example, take a 1m x 1m sample and weigh it. The area is calculated without taking into account ribs, grooves, embossments, etc. For example, a 1m x 1m sample of ribbed separator will have the same area as a 1m x 1m sample of flat separator.

[0095] Example The following examples illustrate methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods, compositions, and results. These examples are not intended to exclude equivalents and variations of the present invention that would be apparent to one skilled in the art.

[0096] Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in degrees Celsius (°C) or is ambient temperature, and pressure is at or near atmospheric. There are many variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction regions and conditions that can be used to optimize product purity and yields resulting from the described processes. Optimization of such process conditions will require no more than reasonable and routine experimentation.

[0097] In this example, antimony (Sb) screening was performed on a flexible separator according to the present invention (Example 1) compared to a conventional flexible rubber separator traditionally used in golf cart battery applications (Control 1). Specifically, the separator leachate production included: A 5 g separator sample is taken by cutting. The sample is immersed in 250 ml of sulfuric acid with a specific gravity of 1.26 to 1.28 in a bottle. Place the jar in a 53°C water bath for 7 days. Filter the sample and use the neat (undiluted) leached electrolyte in the electrochemical cell.

[0098] Electrochemical cell setup Lead electrodes are used as the working and counter electrodes, and a mercury / mercury sulfate (Hg / HgSO4) reference electrode is used. The working electrode side is filled with 75 g of leaching solution, and the counter electrode side is filled with 30 g of leaching solution. Perform linear sweep cyclic voltammetry over the desired potential range on a blank solution (sulfuric acid only). Specifically, data was scanned between -1 V vs. Hg / HgSO4 reference electrode and -1.8 V vs. Hg / HgSO4 reference electrode. This voltage region is more negative than the peak of this curve, which indicates the reduction of lead sulfate to lead, and represents overcharging of the negative electrode. The electrolyte is spiked with 100 ppm Sb on the working electrode (sometimes called "WE") side and a CV (cyclic voltammetry) is run again. The leachate results for the separator of Example 1 are compared to the leachate results for the separator of Control 1. Run multiple times if necessary.

[0099] 3A and 3B show linear sweep cyclic voltammetry curves (cyclic voltammograms) for the separator of Example 1 (FIG. 3A) and the separator of Control 1 (FIG. 3B). Both FIGS. 3A and 3B show the results before spiking the electrolyte with 100 ppm Sb. The data show the first four scans over the aforementioned voltage range. The separator leachate shows hydrogen evolution at potentials above 1.4 V in FIGS. 3A and 3B. The separator of Example 1 shows a lower tendency for H evolution compared to the separator of Control 1, and the H evolution current for the separator of Example 1 at the same potential appears to be lower. Therefore, the performance of the separators according to various embodiments described herein is similar to, equal to, or even better than the all-rubber conventional rubber separator of Control 1. These results are surprising for a PE-based separator such as the separator of the present invention of Example 1.

[0100] Figures 4A and 4B show the results after spiking the electrolyte with 100 ppm Sb. Figures 4A and 4B show the first four cycles for the leachates of Example 1 and Control 1, respectively, and the data show an approximately four-fold increase in current due to hydrogen evolution. The trend in hydrogen evolution (an indicator of Sb suppression) is nearly the same for both samples, which is a surprising result for a PE-based separator such as the inventive separator of Example 1.

[0101] Figure 5 shows a graph comparing the fourth cycle CV data of a lead electrode in a leachate using the separator of Example 1 with a leachate using the separator of Control 1, before and after the addition of 100 ppm antimony to the leachate. The data show the difference in hydrogen evolution current for the control separator and the separator of the present invention, and how the presence of antimony affects the electrochemistry of the lead electrode (negative electrode). It is clear that in the presence of Sb, the performance of the separator of the present invention is comparable to that of the control separator. And, in the absence of antimony in solution, the separator of the present invention slows hydrogen evolution and increases the potential.

[0102] Additionally, experiments using the separator of the present invention have shown that Sb poisoning is suppressed in batteries using this separator. Sb poisoning manifests as a decrease in the hydrogen evolution overpotential or an increase in the rate of hydrogen evolution due to the electrochemical reduction of water. This overpotential can be measured by measuring the hydrogen evolution current at a constant potential, and such experiments have shown that the separator of the present invention outperforms known separators. In similar experiments, it has also been observed that there is a difference in the large anodic (positive current) peak associated with the CV curve of the battery containing the separator of the present invention. Such a peak is due to the Pb P at the surface of the lead working electrode. This is due to the oxidation of Pb to PbSO4. Furthermore, the conventional comparative separator exhibited a positive shift of 40 to 60 mV in the peak position, which may be due to the presence of Sb on the surface, which chemically converts Pb to PbSO4. In the case of the battery including the separator according to the present invention, a smaller shift in the peak position was observed, indicating the suppression of Sb on the lead surface. This observation, combined with the clear reduction in hydrogen evolution rate, indicates that the separator according to the present invention reduces Sb deposition on the negative electrode (lead electrode).

[0103] Disclosed herein is an improved separator for lead-acid batteries. The separator may include a porous membrane, rubber and / or latex, and at least one performance-enhancing additive or surfactant.

[0104] Selected embodiments of the present invention provide a battery separator having a porous membrane composed of a substrate, a rubber, and at least one performance-enhancing additive. The substrate may be one or more of a polymer, polyolefin, polyethylene, polypropylene, ultra-high molecular weight polyethylene ("UHMWPE"), phenolic resin, polyvinyl chloride ("PVC"), rubber, synthetic wood pulp ("SWP"), lignin, glass fiber, synthetic fiber, cellulosic fiber, and combinations thereof. The rubber may be crosslinked rubber, non-crosslinked rubber, natural rubber, latex, synthetic rubber, and combinations thereof. The rubber may further be methyl rubber, polybutadiene, one or more of chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylic rubber, fluororubber, silicone rubber, copolymer rubber, and any combination thereof. The copolymer rubber may be styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), ethylene / vinyl acetate rubber, and combinations thereof.

[0105] One aspect of the present invention can provide a rubber coated on at least a portion of the surface of a porous membrane or impregnated into at least a portion of a porous membrane. Another aspect of the present invention can provide a rubber mixed with a substrate used to form the porous membrane. A refinement of the exemplary embodiment provides a rubber in the substrate that is at least about 1% by weight and not more than about 50% by weight. A further refinement of the exemplary embodiment provides a rubber in the substrate that is at least about 1% by weight and not more than about 20% by weight.

[0106] In accordance with another aspect of the present invention, the at least one performance enhancing additive is a surfactant, and the surfactant may be any one of a nonionic surfactant, an ionic surfactant, an anionic surfactant, a cationic surfactant, and combinations thereof. According to a refinement of the exemplary embodiment, the at least one performance enhancing additive is present in an amount of at least about 0.5 g / m 2 to about 25g / m2 According to a further refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 20 g / m 2 According to another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 15g / m 2 According to yet another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 10 g / m 2 According to yet another refinement of the exemplary embodiment, the at least one performance enhancing additive is at least about 0.5 g / m 2 to about 6 g / m 2 According to another aspect of the exemplary embodiment, the at least one performance enhancing additive may be a surfactant, a wetting agent, a colorant, an antistatic additive, an antimony suppression additive, a UV protection additive, an antioxidant, or the like, and combinations thereof.

[0107] According to another aspect of the present invention, the substrate comprises any one of silica, dry finely divided silica, precipitated silica, amorphous silica, alumina, talc, fish meal, fish bone meal, and combinations thereof. According to another aspect of the present invention, the substrate comprises a processing plasticizer. The processing plasticizer is a processing oil. , petroleum oil, paraffinic mineral oil, mineral oil, and combinations thereof.

[0108] A refinement of an exemplary embodiment provides a battery separator comprising a mat, such as a fibrous mat, which may include any one of glass fibers, synthetic fibers, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof.

[0109] Another refinement of the exemplary embodiment provides a porous membrane having a backweb thickness of at least about 50 μm to about 500 μm. A further refinement of the exemplary embodiment provides a porous membrane having a backweb thickness of at least about 50 μm to about 350 μm.

[0110] Yet another refinement of the exemplary embodiment provides a porous membrane with ribs, which may be solid ribs, serrated ribs, angled ribs, broken ribs, cross ribs, positive ribs, negative ribs, negative cross ribs, channels, embossments, protrusions, bumps, and combinations thereof. The ribs may also be made of rubber. Exemplary separators may be in various shapes or configurations, such as cut pieces, pockets, sleeves, wraps, envelopes, and hybrid envelopes.

[0111] Another aspect of the present invention provides a lead-acid battery having a positive electrode, a negative electrode adjacent to the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte substantially submerging at least a portion of the positive electrode, at least a portion of the negative electrode, and at least a portion of the separator. An exemplary separator may have a porous membrane comprised of a substrate, at least one performance-enhancing additive, and a rubber. The exemplary lead-acid battery may exhibit reduced water loss, reduced antimony poisoning, increased wettability, faster recharge, improved oxidation stability, reduced float current, reduced end-of-charge current, reduced recharge voltage, and combinations thereof. Exemplary lead-acid batteries may have many applications, such as flat plate batteries, flooded lead-acid batteries, reinforced flooded lead-acid batteries, deep cycle batteries, gel batteries, absorbed glass mat ("AGM") batteries, tubular batteries, inverter batteries, vehicle batteries, starting-lighting-ignition ("SLI") batteries, idle-start-stop ("ISS") batteries, car batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid vehicle batteries, electric vehicle batteries, e-rickshaw batteries, or e-bike batteries. Exemplary lead-acid batteries can operate in a partial state of charge, while running, while stationary, in backup power applications, cycling applications, or combinations thereof.

[0112] An exemplary lead acid battery may further include a mat adjacent to at least one of the positive electrode, the negative electrode, or the separator. An exemplary mat may be a fibrous mat and may be composed of glass fibers, synthetic fibers, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof.

[0113] Yet another aspect of the present invention provides a method for manufacturing an exemplary separator by combining a mixture of one or more substrates, a rubber, and at least one additive and extruding the mixture into a membrane. Yet another aspect of the present invention provides a method for manufacturing an exemplary separator by combining a mixture of a polymer and at least one additive, extruding the mixture into a membrane, and adding the rubber to the membrane. Exemplary methods can add the rubber to the membrane by laminating the rubber to at least a portion of the membrane, impregnating the rubber to at least a portion of the membrane, coating the rubber slurry on at least a portion of the membrane, immersing at least a portion of the membrane in the rubber slurry, or forming rubber ribs on the membrane.

[0114] Another alternative embodiment of the present invention is to combine a mixture of one or more base materials and rubber and then mix the mixture. Another method of manufacturing an exemplary separator is provided by extruding a material into a membrane and adding at least one additive to the membrane. Exemplary methods can add at least one additive to the membrane by laminating at least a portion of the membrane with at least one additive, impregnating at least a portion of the membrane with at least one additive, coating at least a portion of the membrane with at least one additive, or soaking the membrane in at least one additive.

[0115] Yet another select embodiment of the present invention provides a method of manufacturing an exemplary separator by combining a mixture of one or more substrates, extruding the mixture into a film, adding a rubber to the film, and adding at least one additive to the film.

[0116] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended to exemplify only a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to be within the scope of the claims. Various composition and method variations in addition to those shown and described herein are intended to be within the scope of the appended claims. Furthermore, while only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of compositions and method steps, even if not specifically recited, are intended to be within the scope of the appended claims. Thus, although combinations of steps, elements, components, or structures are explicitly or hereafter referred to herein, other combinations of steps, elements, components, and structures are also included even if not explicitly stated. As used herein, the term "comprising" and variations thereof are used synonymously with the term "including" and variations thereof and are open or non-limiting terms. Although the terms "comprising" and "including" are used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, which are also disclosed. Except in the examples or where noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims should, at a minimum, be construed in light of the number of significant digits and ordinary rounding approaches, but rather than being construed as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.

[0117] According to at least selected embodiments, aspects, or objectives, disclosed or provided herein are new or improved separators, battery separators, reinforced flooded battery separators, batteries, cells, and / or methods of making and / or using such separators, battery separators, reinforced flooded battery separators, cells, and / or batteries. According to at least certain embodiments, the disclosure or invention relates to new or improved battery separators for reinforced flooded batteries. Also disclosed herein are methods, systems, and battery separators having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, the disclosure or invention relates to improved separators for reinforced flooded batteries, the separators having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, separators are provided that include or exhibit reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, separators are provided that are suitable for flat plate batteries, tubular batteries, SLI for vehicles, and HEV ISS. Separators are provided for battery applications such as for powertrain applications, deep cycle applications, batteries for golf cars or golf carts and e-rickshaws, batteries operating at partial state of charge ("PSOC"), inverter batteries, storage batteries for renewable energy sources, and any combination thereof.

[0118] The present invention may be embodied in other forms without departing from the spirit and essential attributes thereof, and therefore, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the present invention. Components that can be used to perform the disclosed methods and systems are disclosed. These and other components are disclosed herein, and when combinations, subsets, interactions, groups, etc. of these components are disclosed, it is understood that specific reference to their various individual and collective combinations and permutations is not expressly disclosed, but each is specifically contemplated and described herein for all methods and systems. This applies to all aspects of the present application, including, but not limited to, steps in the disclosed methods. Thus, where there are various additional steps that may be performed, it is understood that each of these additional steps may be performed with any specific embodiment or combination of embodiments of the disclosed methods.

[0119] The foregoing descriptions of structures and methods have been presented for purposes of illustration only. The examples disclose exemplary embodiments, including the best mode, and also serve to enable any person skilled in the art to practice the invention, including making and using any device or system, and performing any incorporated methods. These examples are not intended to be exhaustive or to limit the invention to the precise steps and / or forms disclosed. Numerous modifications and variations are possible in light of the above teachings. The features described herein may be combined in any combination. The steps of methods described herein may be performed in any sequence that is physically possible. The patentable scope of the invention is defined by the appended claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that are the same as the claim language, or if they include equivalent structural elements that have insubstantial differences from the claim language.

[0120] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended to exemplify only a few aspects of the claims. Any compositions and methods that are functionally equivalent are intended to be within the scope of the claims. Various composition and method variations in addition to those shown and described herein are intended to be within the scope of the appended claims. Furthermore, while only certain representative compositions and method steps disclosed herein have been specifically set forth, other combinations of compositions and method steps, even if not specifically recited, are intended to be within the scope of the appended claims. Thus, although combinations of steps, elements, components, or structures are referred to herein, either explicitly or infra, other combinations of steps, elements, components, and structures are also included, even if not explicitly stated.

[0121] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the aforementioned "about," it is understood that the particular value forms another embodiment. It is further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. "Optional" or "optionally" means that the ranges may be varied in any manner, provided that the subsequently described events or circumstances occur. This means that the event or circumstance may or may not occur, and that the description includes cases where the event or circumstance occurs and cases where it does not occur.

[0122] Throughout the description and claims of this specification, the word "comprise" and variations of this word, such as "comprising" and "comprises," mean "including but not limited to" and are not intended to exclude, for example, other additives, ingredients, integers, or steps. The terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the invention, which are also disclosed. "exemplary" or "for example" means "an example of" and is not intended to convey that a preferred or ideal embodiment is indicated. Similarly, "such as" is not intended to convey that a preferred or ideal embodiment is indicated. "as") is not used in a limiting sense, but for descriptive or illustrative purposes.

[0123] Except as noted, all numbers expressing shapes, dimensions, and the like used in the specification and claims should, at the very least, be construed in light of the number of significant digits and ordinary rounding approaches, and not be construed as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.

[0124] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference.

[0125] Additionally, any invention illustratively disclosed herein suitably may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. 1. A battery separator, comprising: A porous membrane comprising a backweb and ribs on at least one surface of said web, said porous membrane comprising a polyolefin substrate comprising ultra-high molecular weight polyethylene having a weight molecular weight of 1,000,000 or greater, 1 to 50 weight percent natural rubber, and at least one performance enhancing additive; the at least one performance-enhancing additive is a surfactant, the surfactant comprising one of the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and combinations thereof; The surfactant is 0.5 g / m ２ ~20g / m ２ is present in an amount of A battery separator for use in a lead-acid battery, wherein the back web has a thickness of 50 μm to 350 μm, and a breaking rib is disposed on a surface of the back web at an angle of 60 to 30° relative to an edge of the separator.

2. 2. The battery separator for use in a lead acid battery according to claim 1, wherein said natural rubber is impregnated into at least a portion of said porous membrane.

3. 10. The battery separator for use in a lead acid battery according to claim 1, wherein said natural rubber is mixed with said polyolefin substrate used to form said porous membrane.

4. 4. The battery separator for use in a lead acid battery according to claim 3, wherein said natural rubber is present in an amount of from 1% to 20% by weight based on the weight of said polyolefin substrate.

5. 10. The battery separator for use in a lead acid battery of claim 1, further comprising one or more of the group consisting of a wetting agent, a colorant, an antistatic additive, an antimony inhibitor additive, a UV protection additive, an antioxidant, and combinations thereof.

6. 10. The battery separator for use in a lead acid battery of claim 1 further comprising a mat.

7. 7. The battery separator for use in a lead acid battery according to claim 6, wherein the mat comprises one of the group consisting of glass fibers, synthetic fibers, silica, at least one performance enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof.

8. 10. The battery separator for use in a lead acid battery of claim 1, wherein the porous membrane has formed on its surface facing the positive electrode ribs that are one of the group consisting of solid ribs, serrated ribs, angled ribs, broken ribs, cross ribs, channels, embossments, protrusions, bumps, and combinations thereof.

9. A lead-acid battery comprising the battery separator for use in the lead-acid battery according to any one of claims 1 to 8.

10. combining a polyolefin base material including polyethylene, 1 to 50 wt. % of a natural rubber selected from the group consisting of natural rubber including polyisoprene and latex, and a mixture of surfactants; extruding the mixture into a membrane having a backweb thickness of 50 μm to 350 μm; forming a plurality of breaking ribs on the surface of the back web at an angle of 60 to 30 degrees relative to the edge of the separator; Including, The surfactant comprises one of the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and combinations thereof, and the surfactant is present in an amount of 0.5 g / m ２ ~20g / m ２ 10. The method of claim 1, wherein the amount of

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