Battery separators and lead-acid batteries

Abstract

To provide batteries having reduced acid stratification, mitigating the formation of dendrites, and / or having improved cycling performance.SOLUTION: Disclosed herein are improved separators for lead acid batteries. The separators may include a porous membrane, a rubber, and at least one performance enhancing additive, positive and / or negative electrode ribs, and / or lowered acid-leachable total organic carbon.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators for lead-acid batteries, e.g., flooded lead-acid batteries, and particularly high performance flooded lead-acid batteries ("EFB"), as well as various other lead-acid batteries, e.g., gel and absorbent glass mat ("AGM") batteries. According to at least selected embodiments, the present disclosure or invention is directed 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 improving battery life; reducing battery failure; reducing water loss; improving oxidative 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 wetting time; reducing battery formation time; reducing antimony poisoning; reducing acid stratification; improving acid diffusion and / or improving uniformity in lead-acid batteries; and any combination thereof. According to at least certain embodiments, the present disclosure or invention is directed to an improved separator for lead-acid batteries, the separator comprising 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, for example, in prime movers, such as golf carts (sometimes referred to as golf cars); inverters; and renewable and / or alternative energy systems, such as solar and wind systems. The disclosed separators are also useful in battery systems where deep cycle and / or charging operating conditions are essential for the battery application.In certain other embodiments, the disclosed separators may be used in battery systems in which additives and / or alloys (antimony being a prime example) are added to the battery to improve the battery's life and / or performance and / or to improve the battery's deep cycle and / or charge operating capacity fractional state. [Background technology]

[0002] Battery separators are used to separate the positive and negative electrodes or plates of a battery to prevent electrical shorts. Such battery separators are typically porous to allow ions to pass between the positive and negative electrodes or plates. In lead-acid batteries, such as vehicle batteries and / or industrial batteries and / or deep-cycle batteries, the battery separator is typically a porous polyethylene separator; in some cases, such separators may include a backweb and multiple 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 made in continuous lengths and rolled, then folded and sealed along the edges to form a pouch or envelope that contains the battery electrodes. Certain separators for industrial (or traction or deep cycle) batteries are cut to approximately the same size as the electrode plates (strips or foils).

[0003] Electrodes in lead-acid batteries are often constructed of lead alloys with relatively high antimony content. Batteries operated at partial state of charge ("PSOC") tend to develop acid stratification. In this condition, more acid is concentrated in the electrolyte at the bottom of the battery, and more water is concentrated in the electrolyte at the top of the battery. Lead becomes soluble in water and goes into solution. However, such lead precipitates in the acid, forming solid crystals. Acid stratification therefore tends to cause the formation of lead sulfate (Pb2SO4) crystals that form dendrites. Even without acid stratification, the acid can be depleted during discharge, bringing the lead into solution, and then precipitate out as crystals as the acid is restored during the charge cycle.

[0004] When these crystals build up to a large enough size, the dendrites can puncture or dissolve the separator, forming a bridge connecting the negative electrode to the positive electrode, causing a short circuit. This can prevent voltage discharge, charge acceptance, or even cause catastrophic failure, rendering the battery non-functional. Any of these can impair the battery's performance and lifespan.

[0005] There remains a need for improved separators that provide improved cycle life, reduced acid stratification, and / or reduced dendrite formation, at least in certain applications or batteries. More particularly, there remains a need for improved separators, and improved batteries (e.g., those operating in a partial state of charge) that provide increased battery life, reduced battery failure, improved oxidation stability, improved, maintained, and / or lower float current, improved end-of-charge ("EOC") current, reduced current and / or voltage required to charge and / or fully charge deep cycle batteries, minimized internal electrical resistance increase, lower electrical resistance, reduced antimony poisoning, reduced acid stratification, improved acid diffusion, and / or improved uniformity in lead-acid batteries. Summary of the Invention [Problem to be solved by the invention]

[0006] The details of one or more embodiments are set forth in the detailed description below. Other features, objects, and advantages are apparent from the detailed description and claims. According to at least selected embodiments, the present disclosure or invention may address the above-mentioned problems or needs. 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 acid stratification, mitigated dendrite formation, and / or improved cycling performance. [Means for solving the problem]

[0007] According to at least selected embodiments, the present disclosure or invention is directed 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 is directed to new or improved battery separators for flat plate batteries, tubular batteries, flooded lead acid batteries, advanced flooded lead acid batteries ("EFB"), deep cycle batteries, gel batteries, absorbent glass mat ("AGM") batteries, inverter batteries, solar or wind storage batteries, vehicle batteries, start-up light ignition ("SLI") vehicle batteries, stop-start ("ISS") vehicle batteries, automobile batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric bicycle batteries, and / or improved methods of making and / or using such improved separators, cells, batteries, systems, etc. It also improves battery performance and life, reduces battery failure, reduces acid stratification, reduces dendrite formation, improves oxidation stability, improves, maintains, and / or reduces float current, improves end-of-charge current, reduces the current and / or voltage required to charge and / or fully charge deep cycle batteries, reduces internal electrical resistance, reduces antimony poisoning, increases wettability, improves acid diffusion, and improves lead-acid Disclosed herein are methods, systems, and battery separators for improving uniformity in batteries and / or improving cycling performance. According to at least certain embodiments, the disclosure or invention is directed to improved separators, where the novel separators include reduced electrical resistance, performance-enhancing additives or coatings, improved fillers, increased wettability, increased acid diffusion, negative electrode cross ribs, and the like. In at least one very specific embodiment, the present disclosure or invention is directed to an improved separator, wherein the novel separator comprises or has an acid leachable total organic carbon (“TOC”) of approximately 2,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, more preferably approximately 1,500 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and even more preferably approximately 1,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and an anode rib extending from the anode opposite the surface of the porous membrane, preferably a plurality of ribs as TD or cross MD anode mini-ribs, and even more preferably anode cross ribs, that are designed and optimized to reduce dendrite formation and growth.

[0008] To achieve these and other objectives, in certain select embodiments, a separator having a porous membrane and an optional fibrous mat (laminated or otherwise adjacent to the porous membrane) is proposed for use in a lead-acid battery, e.g., an EFB or deep-cycle battery, having a negative and positive electrode with the separator disposed therebetween. One or both of the porous membrane or the fibrous mat may comprise natural and / or synthetic rubber and at least one performance-enhancing additive impregnated or coated into or on at least a portion of either side of either the porous membrane or the fibrous mat. Additionally, the porous membrane may comprise ribs on either or both sides thereof in various patterns and orientations.

[0009] According to selected embodiments, an improved or new battery separator includes a porous membrane having a backweb with a plurality of ribs extending from at least a portion of the backweb. The porous membrane may include a composition of a polymer, a filler, at least one performance-enhancing additive, a plasticizer, and optionally a rubber. The separator may have an acid-leachable total organic carbon ("TOC") of approximately 2,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, preferably approximately 1,500 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and more preferably approximately 1,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber.

[0010] Selected embodiment refinements may provide at least some of the ribs as positive electrode ribs extending from the positive electrode facing the surface of the porous membrane, and at least some of the ribs as negative electrode ribs extending from the negative electrode facing the surface of the porous membrane, or embodiments may include both positive and negative electrode ribs. Either or both of the positive and negative electrode ribs may extend uniformly from the first lateral edge to the second lateral edge, or none may extend uniformly from the first lateral edge to the second lateral edge. Either or both of the positive and negative electrode ribs may extend uniformly from the top edge to the bottom edge, or none may extend uniformly from the top edge to the bottom edge. Either or both of the positive and negative electrode ribs may be designed and optimized to reduce dendrite formation and growth.

[0011] In certain exemplary separators, any positive and / or negative ribs The set may be any one of the following: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, slanted ribs, linear ribs, ribs extending longitudinally in a substantially machine direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending transversely in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag sawtooth ribs, broken discontinuous zigzag sawtooth ribs, grooves, channels, textured regions, embossments, dimples, cylinders, miniature cylinders, porous, non-porous, intersecting ribs, miniature ribs, intersecting miniature ribs, and combinations thereof.

[0012] In select exemplary separators, any positive and / or negative rib set may be a broken rib, with the rib having a distinct end point contained within the separator edge and disconnected from any other rib. The broken rib may be defined by an angular orientation that improves acid mixing in the battery, particularly during battery operation, with the separator disposed therein and positioned parallel to the battery's start and stop motion. The angular orientation may be defined relative to the separator's MD and may be an angle between zero degrees (0°) and less than 180 degrees (180°), or between 180 degrees (180°) and less than 360 degrees (360°). The angular orientation of the ribs may vary across multiple ribs. In certain select embodiments, exemplary separators may have multiple rib sets, with each rib set having a different or the same angular orientation compared to the other rib sets. In other exemplary separators, the positive and / or negative electrode ribs may have an angular orientation that is between zero degrees (0°) and three hundred sixty degrees (360°).

[0013] In select embodiments, the positive electrode ribs may have a rib height of approximately 50 μm to approximately 2.0 mm. Additionally, at least some of the positive electrode ribs may have a base width of approximately 300 μm to approximately 750 μm. In some exemplary embodiments, at least some of the positive electrode ribs may have a second base width of approximately 400 μm to approximately 500 μm. When at least some of the positive electrode ribs and / or negative electrode ribs are substantially straight and substantially parallel to each other, they may have a spacing length of approximately 50 μm to approximately 20 mm.

[0014] In certain exemplary embodiments, the height of the negative electrode rib may be approximately 5.0% or less to approximately 100% or more of the height of the positive electrode rib. For example, a battery separator may have negative electrode ribs with a height range of approximately 5.0 μm to approximately 2.0 mm. Exemplary negative electrode ribs may have a base width of approximately 5 μm to approximately 500 μm.

[0015] In selected exemplary embodiments, aspects of the present invention provide a separator or porous membrane having a composition that may include any or more of the following: 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, cellulose fiber, rubber, and combinations thereof.

[0016] The improvement of the present invention provides that the rubber may be any one or more of the following: crosslinked rubber, non-crosslinked rubber, cured rubber, non-cured rubber, natural rubber, latex, synthetic rubber, and combinations thereof. Another improvement of the present invention provides that the rubber may be any one or more of the following: methyl rubber, polybutadiene, one or more chloroprene rubbers, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, silicone rubber, copolymer rubber, and combinations thereof. Furthermore, the copolymer rubber may be any one or more of the following: styrene / butadiene rubber, acrylonitrile rubber, styrene / butadiene rubber, acrylic ... The rubber may be any one or more of: ethylene / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), ethylene / vinyl acetate rubber, and combinations thereof.

[0017] In select embodiments, the rubber may be present in an amount that is about 1% to about 6% by weight, preferably about 3% by weight, preferably about 6% by weight, and more preferably about 3% to about 6% by weight. The rubber may be mixed with other substrates of the separator or coated onto at least a portion of one or more surfaces of the separator or porous membrane. When coated, the rubber may be applied as a liquid slurry and dried.

[0018] Exemplary embodiments of the present invention may possess a filler that may be any one or more of the following: silica, dry finely divided silica; precipitated silica; amorphous silica; alumina; talc; fish meal, fish bone meal, and combinations thereof. Further, the silica may be in the range of about 21:100 to 35:100, about 23:100 to about 31:100, about 25:100 to about 29:100, or alternatively at least about 27:100 or greater. 29 It may have a molar ratio of OH:Si groups as determined by Si-NMR.

[0019] Exemplary fillers of the present invention may provide exemplary fillers with high structural morphology. The improvements of the present invention include: having an average particle size of 5 μm or less; 2 / g Exemplary fillers may be provided that are characterized by one of the group consisting of: having a surface area; having an oil absorption rate of at least 150 ml / 100 mg; and combinations thereof.

[0020] The separator or porous membrane may have a filler to polymer (filler:polymer) weight ratio of about 2.0:1.0 to about 4.0:1.0, for example, about 2.0:1.0; alternatively, about 2.6:1.0; also alternatively, such as about 3.5:1.0; and a filler to combination of filler and rubber (filler:polymer and rubber) by weight of about 2.0:1.0 to about 3.0:1.0, for example, 2.6:1.0.

[0021] Exemplary porous membranes can have a backweb thickness of from about 50 μm to about 400 μm, preferably from about 75 μm to about 250 μm, preferably from about 100 μm to about 200 μm, preferably from about 100 μm to about 150 μm, and most preferably from about 75 μm to about 125 μm.

[0022] Exemplary separators according to the present disclosure may have an overall thickness of from about 100 μm to about 1.0 mm, preferably from about 100 μm to about 850 μm, preferably from about 100 μm to about 650 μm, preferably from about 100 μm to about 450 μm, preferably from about 100 μm to about 250 μm, and most preferably from about 100 μm to about 150 μm.

[0023] Another aspect of the present invention may provide at least one performance-enhancing additive, which may be one or more of the following: surfactants, wetting agents, colorants, antistatic additives, antimony suppression additives, UV-protection additives, antioxidants, and combinations thereof. The improvement provides that exemplary surfactants are one or more of the following: nonionic surfactants, ionic surfactants, anionic surfactants, cationic surfactants, and combinations thereof. Furthermore, exemplary performance-enhancing additives may possess lithium ions, aluminum ions, or both.

[0024] Exemplary embodiments are at least approximately 0.5 g / m 2 ~approximately 6g / m 2 , alternatively , approximately 0.5 g / m 2 ~approximately 3g / m 2 The performance-enhancing additive may be, for example, coated on at least a portion of the porous membrane or separator, impregnated within at least a portion of the porous membrane or separator, or mixed with the polymer and filler prior to extrusion of the porous membrane.

[0025] Another aspect of the present invention provides a porous membrane or separator comprising a processing plasticizer, which may be, for example, processing oil, petroleum oil, paraffinic mineral oil, mineral oil, and combinations thereof. The plasticizer is typically added to the mixture of polymer, filler, and optional performance-enhancing additives prior to extrusion of the porous membrane. After extrusion, a portion of the plasticizer may be extracted by known means.

[0026] In some select embodiments, the separator further comprises a fibrous mat that may be attached or adhered to the separator in some manner or simply disposed adjacent thereto. The mat may be composed of any one or more of the following: glass fiber, synthetic fiber, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, or a combination thereof. The mat may also be a nonwoven fabric, a woven fabric, a fleece, a net, or a combination thereof.

[0027] Exemplary separators may exhibit improved performance parameters, such as lower electrical resistance ("ER"), compared to conventional separators. For example, the ER may be approximately 65 mΩ·cm. 2 Less than or equal to 50 mΩ·cm, preferably 2 Less than or equal to approximately 35 mΩ·c, most preferably m 2 It may be the following:

[0028] Exemplary separators may include a conductive layer on one or both of the positive and negative electrode sides of the separator. The separator may also have an oxidation resistance of approximately 200% or greater at 40 hours. Furthermore, separators may take on various shapes and / or configurations. For example, exemplary separators may be any one of the following: cut pieces, pockets, sleeves, wraps, envelopes, hybrid envelopes, S-woven separators, or include side folds.

[0029]

[0010] Embodiments of the present invention also provide batteries using separators substantially as described herein. For example, the battery may be a lead-acid battery, such as a flat-plate battery, a flooded lead-acid battery, an advanced flooded lead-acid battery ("EFB"), a deep-cycle battery, a gel battery, an absorbent glass mat ("AGM") battery, a tubular battery, an inverter battery, a vehicle battery, a start-stop light ignition ("SLI") vehicle battery, an idle-stop ("ISS") vehicle battery, a car battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric vehicle battery, an electric rickshaw battery, an electric bicycle battery, an uninterruptible power supply ("UPS") battery, or a solar or wind or other renewable energy storage system battery. Exemplary batteries may be used at a partial state of charge with a possible depth of discharge of between approximately 1% and approximately 99%, possibly between approximately 1% and approximately 50%, and additionally between approximately 50% and approximately 99%. Batteries may be utilized in driving, stationary, energy storage system applications; renewable energy storage system applications; continuous power supply applications; energy storage system applications, backup power applications, cycling applications, and combinations thereof.

[0030] Other embodiments may include systems including a battery substantially as described herein. Such systems may include energy storage systems; renewable energy storage systems; continuous power supplies; energy storage systems, backup power systems, and combinations thereof. Such systems may be mounted on vehicles, e.g., automobiles, trucks, motorcycles, etc. , all-terrain vehicles, forklifts, golf carts, hybrid automobiles, hybrid electric vehicle batteries, electric vehicles, idle-stop (“ISS”) vehicles, water containers, electric rickshaw batteries, electric tricycles, and electric bicycle batteries.

[0031] In certain preferred embodiments, the present disclosure or invention provides a flexible battery separator that unexpectedly addresses a previously unmet need in the deep-cycle battery industry through an improved battery separator (a porous membrane of a polymer, e.g., polyethylene, plus a specified amount of performance-enhancing additives and ribbing) with a synergistic combination of components and physical attributes and characteristics that meet, and in certain embodiments, exceed, the performance of previously known flexible separators currently used in many deep-cycle battery applications. In particular, the inventive separators described herein are more robust, less brittle, less brittle, and more stable (less susceptible to degradation) over time than separators conventionally used by deep-cycle batteries. The flexible, performance-enhancing additive-containing separators and ribbed separators of the present invention combine the desirable robust physical and mechanical properties of polyethylene-based separators with conventional separators, while also improving the performance systems of batteries using them. [Brief explanation of the drawings]

[0032] [Figure 1A] FIG. 1A illustrates the basic physical features of an exemplary battery separator of the present invention. [Figure 1B] FIG. 1B illustrates the basic physical features of an exemplary battery separator of the present invention. [Figure 1C] FIG. 1C illustrates the basic physical features of an exemplary battery separator of the present invention. [Figure 2A] FIG. 2A shows various exemplary separators with different ribs on the negative surface of the backweb, including optional flat backweb voids of the ribs, and their possible effect on dendrite growth. [Figure 2B] FIG. 2B shows various exemplary separators with different ribs on the negative surface of the backweb, including optional flat backweb voids of the ribs, and their possible effect on dendrite growth. [Figure 2C]FIG. 2C shows various exemplary separators with different ribs on the negative surface of the backweb, including optional flat backweb voids of the ribs, and their possible effect on dendrite growth. [Figure 3A] FIG. 3A illustrates various exemplary rib shapes according to the present invention. [Figure 3B] FIG. 3B illustrates various exemplary rib shapes according to the present invention. [Figure 3C] FIG. 3C illustrates various exemplary rib shapes according to the present invention. [Figure 3D] FIG. 3D illustrates various exemplary rib shapes according to the present invention. [Figure 4A] FIG. 4A shows a general depiction of various rib patterns of an exemplary battery separator of the present invention. [Figure 4B] FIG. 4B shows a general depiction of various rib patterns of an exemplary battery separator of the present invention. [Figure 4C] FIG. 4C shows a general depiction of various rib patterns of an exemplary battery separator of the present invention. [Figure 4D] FIG. 4D shows a general depiction of various rib patterns of an exemplary battery separator of the present invention. [Figure 4E] FIG. 4E shows a general depiction of various rib patterns of an exemplary battery separator of the present invention. [Figure 5] Figure 5 shows the silica size before and after sonication and further shows the particle size distribution of the novel and standard silicas before sonication and after 30 and 60 seconds of sonication. [Figure 6A] FIG. 6A is a schematic rendering of the extension test sample. [Figure 6B] FIG. 6B shows the sample holder for extension testing. DETAILED DESCRIPTION OF THE INVENTION

[0033] According to at least selected embodiments, the present disclosure or invention may address the above-mentioned problems or needs. 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 acid stratification, mitigated dendrite formation, and / or improved cycling performance.

[0034] According to at least selected embodiments, the present disclosure or invention is directed 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 is directed to new or improved battery separators for flat plate batteries, tubular batteries, flooded lead acid batteries, advanced flooded lead acid batteries ("EFB"), deep cycle batteries, gel batteries, absorbent glass mat ("AGM") batteries, inverter batteries, solar or wind storage batteries, vehicle batteries, start-up light ignition ("SLI") vehicle batteries, stop-start ("ISS") vehicle batteries, automobile batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric bicycle batteries, and / or improved methods of making and / or using such improved separators, cells, batteries, systems, etc. Also disclosed herein are methods, systems, and battery separators for improving battery performance and life, reducing battery failure, reducing acid stratification, mitigating dendrite formation, improving oxidative stability, improving, maintaining, and / or lowering float current, improving end-of-charge current, reducing the current and / or voltage required to charge and / or fully charge a deep cycle battery, reducing internal electrical resistance, reducing antimony poisoning, increasing wettability, improving acid diffusion, improving uniformity in lead-acid batteries, and / or improving cycling performance. According to at least certain embodiments, the present disclosure or invention is directed to improved separators, wherein the novel separators include reduced electrical resistance, performance-enhancing additives or coatings, improved fillers, increased wettability, increased acid diffusion, negative electrode cross ribs, and the like.In at least one very specific embodiment, the present disclosure or invention is directed to an improved separator, wherein the novel separator comprises or has an acid leachable total organic carbon (“TOC”) of approximately 2,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, preferably approximately 1,500 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and more preferably approximately 1,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and a plurality of ribs as anode ribs extending from the surface of the porous membrane, preferably TD (or cross MD) anode mini-ribs, and even more preferably anode cross ribs (NCR), that are designed and optimized to add strength, reduce acid stratification, aid in gas release, and / or reduce dendrite formation and growth.

[0035] physical properties Exemplary separators may comprise webs of porous membranes, e.g., microporous membranes having pores less than about 5 μm, preferably less than about 1 μm, mesoporous membranes, or macroporous membranes having pores greater than about 1 μm. The porous membranes may preferably have pore sizes ranging from submicron up 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 vary in certain embodiments. In certain select embodiments, the porous membrane may be flat or have ribs extending from its surface. As shown in FIGS. 1A-1C, the separator may be defined by various dimensions, which are described in detail below. For example, the separator may have a backweb thickness Tback, a total thickness Ttotal, a positive rib height Hcath, a positive rib bottom width Wcath, an optional second positive rib bottom width W'cath (shown in FIG. 1D), a positive rib pitch Pcath, a negative rib height Hnag, a negative rib bottom width Wnag, a negative rib bottom width Wnag, and a negative rib pitch Pnag.

[0036] 1A-1C, an exemplary separator 100 comprises a web of porous membrane 102. Separator 100 and membrane 102 have a machine direction ("MD") and a cross-machine direction ("CMD"), a top edge 101 and a bottom edge 103 (both substantially parallel to the CMD), and side edges 105a, 105b (both substantially parallel to the MD).

[0037] Referring to FIG. 1A, separator 100 includes a positive electrode surface, so named because it faces a positive electrode (not shown) when separator 100 is disposed in a battery (not shown). FIG. 1A shows the positive electrode surface of the separator. One or more first or positive electrode rib sets 104 may be provided and may extend from at least a portion of the positive electrode surface of porous membrane 102. As shown, ribs 104 are solid and disposed in membrane 102 in a substantially longitudinal direction, substantially parallel to separator MD. Positive electrode ribs 104 are also shown to extend uniformly across the entire separator width W from lateral edge 105a to lateral edge 105, known as a "universal profile." As shown in FIG. 1C, the separator has a width W, which, at least in selected embodiments, may range from approximately 40 mm to approximately 170 mm, depending on the type of battery in which separator 100 is used.

[0038] Referring to FIG. 1B, separator 100 includes a negative electrode surface, so named because it faces a negative electrode (not shown) when separator 100 is disposed in a battery (not shown). FIG. 1B shows the negative electrode surface of the separator. One or more sets of second or negative electrode ribs 106 may be provided and may extend from at least a portion of the negative electrode surface of porous membrane 102. As shown, ribs 104 are solid and disposed in an orthogonal orientation to positive electrode ribs 104, which are substantially parallel to separator CMD. Thus, the ribs may be laterally disposed as described above and may be referred to as cross ribs, or negative electrode cross ribs ("NCR(s)"). Negative electrode ribs 106, however, need not be orthogonal to positive electrode ribs 104. They may be the same size, larger, or smaller, in the same or different patterns, or combinations thereof.

[0039] Lead goes into solution in an aqueous environment and then precipitates in the acid. A typical lead-acid battery has an electrolyte of sulfuric acid solution with a specific gravity of approximately 1.28. Lead-acid batteries become acid-starved during discharge cycles, meaning that the acid in the electrolyte is consumed in a reaction, leaving the electrolyte with a higher water content (i.e., a lower specific gravity). Furthermore, batteries operating at partial state of charge ("PSOC") are prone to acid stratification. Acid stratification is a condition in which the acid (which is more concentrated than water) in the electrolyte solution falls and collects at the bottom of the battery, leaving the water content in the electrolyte at the top of the battery higher. Acid stratification can be alleviated when the battery is overcharged or kept at or near 100% charged capacity. However, many batteries do not operate at 100% charged capacity.

[0040] Deep cycle batteries, such as those used in golf carts, forklifts, electric rickshaws, electric bicycles, idle-stop ("ISS") vehicles, etc., operate nearly constantly in a partial state of charge. Such batteries, with the possible exception of ISS batteries, operate at a constant rate of charge. These batteries are typically discharged for 8 to 12 hours or more before being returned to service. Furthermore, operators of these batteries may not overcharge them before returning them to service. ISS batteries undergo cycles of discharge and short intermittent charge cycles, and generally rarely achieve full charge or are overcharged. These batteries and others are prone to acid deficiency, acid stratification, or both. These batteries are therefore subjected to cycles (or regions within the battery) where the electrolyte has a high water concentration. These batteries are also subjected to cycles (or regions within the battery) where the electrolyte has a higher acid concentration. As a result, lead in the electrodes has the opportunity to go into solution in the electrolyte and then precipitate as lead sulfate (Pb2SO4) crystals. Over time, and through many discharge-charge cycles, lead sulfate crystals build up on the surface of the negative electrode and build up on themselves, forming dendrites. Severe or large dendrites are large enough to melt the separator, connect the positive and negative electrodes, and short-circuit the battery cell. This can lead to total battery failure, or at least to poor performance and shortened battery life.

[0041] The inventors hypothesize that dendrites begin to form at the negative electrode and grow toward the positive electrode. The inventors further hypothesize that the porous to microporous structure of the separator acts as something of a framework, providing the lead sulfate crystals with a structure that will be built up. As the lead sulfate crystals begin to form at the negative electrode, they may attach to the separator and build up on them. Over time, the crystals fill the separator's porous structure, forming tiny dendrites that cause micro-short circuits, which can hinder battery performance and lead to total battery failure. The inventors propose a solution to this problem by reducing contact between the separator and the electrode, preferably between the separator and the negative electrode, although the contact area between the separator and the positive electrode can also be reduced. Reducing the contact area between the separator and the electrodes can also help reduce acid stratification, improve acid mixing, improve the acid reservoir next to the plate or electrode, aid in gas release, provide more uniform charging across the plate, and combinations thereof.

[0042] 2A-2C illustrate various scenarios for dendrite formation. The figures show various embodiments of a separator 100 disposed between an anode 202 and a cathode 204. While all separators have cathode ribs 104, only FIGS. 2B and 2C show the separator 100 with an anode 106. The inventors believe that the more contact there is between the separator 100 and the anode 202, the more likely dendrites 206 are to form and grow within the porous structure. As shown in FIG. 2A, the backweb 102 has a flat surface facing the anode 202. The inventors hypothesize that dendrites 206 have more opportunities to grow and form bridges between the anode 202 and the cathode 204 within the separator 100. FIG. 2B shows a separator 100 with negative electrode cross ribs 106, which reduces the contact area between the separator 100 and the negative electrode 202, reducing the opportunity for dendrites 206 to form and grow within the separator 100 and bridge between the two electrodes 202, 204. As shown in FIG. 2C, the separator 100 has fewer negative electrode cross ribs 106 than those shown in FIG. 2B, which are farther apart and taller than those shown in FIG. 2B. This results in even less contact between the separator 100 and the negative electrode 202, which in turn results in even less opportunity for dendrites 206 to bridge from the negative electrode 202 and positive electrode 204. We hypothesize that even less opportunity for dendrite 206 growth can be achieved by somehow discontinuing or breaking the contact between the ribs 106 and the electrodes 202. This can be achieved by providing discontinuities, breaks, serrations, or other rib morphology where there are portions of the rib 106 that do not contact the surface of the electrode 202. While these examples focus on the negative electrode ribs 106, the same treatments can be applied to the positive electrode ribs 104.

[0043] rib The ribs 104, 106 may be solid, discrete, broken, continuous, discontinuous, angled, linear, longitudinal ribs extending substantially in the MD of the separator, lateral ribs extending substantially in the width direction CMD of the separator, transverse ribs extending substantially in the CMD of the separator, cross ribs extending substantially in the width direction of the separator, sawtooth or sawtooth ribs, battlemented or battlemented ribs, curved or sinusoidal, solidly disposed or broken zigzag-like forms, grooves, channels, textured regions, embossments, dimples, porous, non-porous, miniature ribs or cross miniature ribs, and the like, and a uniform set, alternating set, or mixture or combination thereof. Additionally, the ribs 104, 106 may extend from or on the positive electrode side, the negative electrode side, or both sides.

[0044] 3A and 3B show exemplary embodiments of a separator backweb 102 having ribs 104 / 106 (either positive or negative ribs) positioned adjacent to electrodes 202 / 204 (either positive or negative). Certain exemplary embodiments of the ribs 104 / 106 (both positive and / or negative ribs) may have a generally triangular shape ( FIG. 3A ) with a rib base width W and a rib height H rib , or a generally semicircular shape ( FIG. 3B ) with a rib base width W and a rib height H rib . As shown in FIG. 3A , the generally triangular shape may be any triangular shape with a single rib base width W, for example, an equilateral triangle, an isosceles triangle, or a scalene triangle. Separators may also have a mixture of separator shapes. As shown in FIG. 3B , the generally semicircular shape may also be an elliptical, oval, or oval shape with a single rib base width W. The purpose of this shape is to reduce contact between the separator and the electrodes 202 / 204.

[0045] Figure 3C shows ribs 104 / 106 having a generally semicircular shape. In this embodiment, ribs 104 / 106 have a first rib base width Wbase and further have an optional second rib base width W'base, which may be considered the neck or necking portion of rib 104. Figure 3D shows ribs 104 / 106 having a generally isosceles triangular shape with a single rib base width Wbase. Exemplary separators may have any mixture of shapes, base widths Wbase, W'base, and rib heights Hrib.

[0046] Referring now to Figures 4A-4E, several embodiments of ribbed separators with different rib profiles are shown. The ribs shown may preferably be cathode ribs 104. The angled rib pattern of Figures 4A-4C may be a possibly preferred Daramic® RipTide™ acid-mixed rib profile, which may help reduce or eliminate acid stratification in certain batteries. In some embodiments, the ribs may be discrete broken ribs with an angular orientation relative to the separator MD. The angular orientation may be between greater than zero degrees (0°) and less than one hundred and eighty degrees (180°), or greater than one hundred and eighty degrees (180°) and less than three hundred and sixty degrees (360°). As further shown in Figures 4A-4C, the ribs may have one or more rib sets, each set having varying angular orientations and locations on the separator. The negative electrode side may have no ribs (smooth), may have the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs or NCR, angled ribs, or a combination thereof.

[0047] Figure 4D shows the profile of a longitudinal sawtooth rib pattern. Figure 4E shows the profile of a sloped offset rib pattern. The negative side may have no ribs (smooth), the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs or NCR, sloped ribs, or a combination thereof.

[0048] As discussed above, the ribs may extend uniformly across the width of the separator from side edge to side edge, known as a universal profile. Alternatively, the separator may have side panels adjacent to its side edges with minor ribs disposed on the side panels. These minor ribs may be spaced closer to and smaller than the first ribs. For example, the minor ribs may be 25% to 50% the height of the first ribs. Alternatively, the side panels may be flat. The side panels may help seal one edge of the separator to another edge of the separator, as occurs when wrapping the separator, as discussed below.

[0049] In select exemplary embodiments, at least some of the cathode ribs may preferably have a height of about 50 μm to about 2.0 mm (H in FIG. 1C). In some exemplary embodiments, the cathode rib height H may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or 2.0 mm. In other exemplary embodiments, the cathode rib height Hcathode may be less than or equal to approximately 2.0 mm, 1.8 mm, 1.6 mm, 1.4 mm, 1.2 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0050] In certain selected embodiments, the positive electrode rib may preferably have a bottom width (W positive electrode bottom in FIG. 1C) of approximately 300 μm to approximately 750 μm. In some exemplary embodiments, the positive electrode rib bottom width may be approximately 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, or 750 μm. In some exemplary embodiments, the positive electrode rib bottom width may be approximately 750 μm, 700 μm, 600 μm, 500 μm, 400 μm, or 300 μm or less.

[0051] In select embodiments, the positive rib may have a second width W' positive base near the base (such as the neck) of about 400 μm to about 500 μm.

[0052] When at least a portion of the positive electrode ribs are substantially straight and substantially parallel to one another, they may have a spacing length or pitch (P positive electrode in FIG. 1C ) of approximately 50 μm to approximately 20 mm. In some exemplary embodiments, the positive electrode rib pitch may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1.0 mm, 2.0 mm, 3.0 mm, 4.0 mm, or 5.0 mm, 6.0 mm, 7.0 mm, 8.0 mm, 9.0 mm, or 10.0 mm, 11.0 mm, 12.0 mm, 13.0 mm, 14.0 mm, or 15.0 mm, 16.0 mm, 17.0 mm, 18.0 mm, 19.0 mm, or 20.0 mm. In other exemplary embodiments, the positive electrode rib pitch may be less than or equal to approximately 20.0 mm, 19.0 mm, 18.0 mm, 17.0 mm, or 16.0 mm, 15.0 mm, 14.0 mm, 13.0 mm, 12.0 mm, or 11.0 mm, 10.0 mm, 9.0 mm, 8.0 mm, 7.0 mm, or 6.0 mm 5.0 mm, 4.0 mm, 3.0 mm, 2.0 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0053] In selected exemplary embodiments, at least some of the negative electrode ribs may preferably have a height of about 5% to about 100% of the height of the positive electrode ribs. In some exemplary embodiments, the negative electrode rib height may be about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95%, or 100% of the positive electrode rib height. In other exemplary embodiments, the negative electrode rib height may be about 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 4 ...0%, 55%, 50%, 50 It may be 0%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% or less.

[0054] In select exemplary embodiments, at least some of the negative electrode ribs may preferably have a height of about 5 μm to about 1.0 mm (H negative electrode in FIG. 1C). In certain embodiments, the negative electrode rib height H negative electrode may be about 5 μm, 10 μm, 25 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or 2.0 mm. In other exemplary embodiments, the cathode rib height H may be less than or equal to approximately 2.0 mm, 1.8 mm, 1.6 mm, 1.4 mm, 1.2 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm, 25 μm, 10 μm, or 5 μm.

[0055] In certain exemplary embodiments, at least some of the negative electrode ribs may preferably have a bottom width of approximately 5 μm to approximately 1.0 mm. For example, the negative electrode bottom width may be approximately 5 μm, 10 μm, 25 μm, 25 μm, 75 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, or 1.0 mm. In other embodiments, the negative electrode bottom width may be less than or equal to approximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 150 μm, 100 μm, 75 μm, 50 μm, 25 μm, 10 μm, or 5 μm.

[0056] When at least a portion of the negative electrode ribs are substantially straight and substantially parallel to one another, they may have a spacing length or pitch of approximately 50 μm to approximately 20.0 mm (P negative electrode in FIG. 1B). In some exemplary embodiments, the negative electrode rib pitch may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1.0 mm, 2.0 mm, 3.0 mm, 4.0 mm, or 5.0 mm, 6.0 mm, 7.0 mm, 8.0 mm, 9.0 mm, or 10.0 mm, 11.0 mm, 12.0 mm, 13.0 mm, 14.0 mm, or 15.0 mm, 16.0 mm, 17.0 mm, 18.0 mm, 19.0 mm, or 20.0 mm. In other embodiments, the negative electrode rib pitch may be equal to or less than approximately 20.0 mm, 19.0 mm, 18.0 mm, 17.0 mm, or 16.0 mm, 15.0 mm, 14.0 mm, 13.0 mm, 12.0 mm, or 11.0 mm, 10.0 mm, 9.0 mm, 8.0 mm, 7.0 mm, or 6.0 mm 5.0 mm, 4.0 mm, 3.0 mm, 2.0 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0057] In some select embodiments, at least a portion of the porous membrane may have longitudinal or transverse anode ribs or cross ribs. The anode ribs may be parallel to the separator's top edge or may be disposed at an angle thereto. For example, the anode ribs may be oriented at approximately 0°, 5°, 15°, 25°, 30°, 45°, 60°, 70°, 80°, or 90° relative to the top edge. The cross ribs may be oriented between approximately 0° and approximately 30°, between approximately 30° and approximately 45°, between approximately 45° and approximately 60°, between approximately 30° and approximately 60°, between approximately 30° and approximately 90°, or between approximately 60° and approximately 90° relative to the top edge.

[0058] Certain exemplary embodiments may possess serrations or serrated ribs. If present, these may have an average tip length of approximately 50 μm to approximately 1.0 mm. For example, the average tip lengths may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or greater. Alternatively, they may be 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less.

[0059] At least some of the serrations or ribs may have an average baseline length of about 50 μm to about 1.0 mm. For example, the average baseline length may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less.

[0060] At least some of the serrations or ribs may have an average height of approximately 50 μm to approximately 1.0 mm. For example, the average height may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be approximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less. In embodiments where the serration height is the same as the rib height, the ribs may also be referred to as protrusions. Such ranges may apply to separators for industrial traction start-stop batteries, where the total separator thickness Ttotal may typically be from about 1 mm to about 4 mm, as well as for automotive start-stop batteries, where the total separator thickness Ttotal is much thinner (e.g., typically from about 0.3 mm to about 1 mm).

[0061] At least some of the serrations or ribs may have an average center-to-center pitch within the longitudinal columns of approximately 100 μm to approximately 50 mm. For example, the average center-to-center pitch may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or greater, and in similar increments up to 50 mm. Alternatively, they may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or less, and in similar increments up to 50 mm. Adjacent columns of serrations or ribs may also be similarly positioned at the same longitudinal or offset locations. In an offset configuration, adjacent serrations or ribs are positioned at different longitudinal positions.

[0062] At least some of the serrations or ribs may have an average height-to-base width ratio of about 0.1:1.0 to about 500:1.0. For example, the average height-to-base width ratio may be about 0.1:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1, 450:1.0, or 500:1.0. Alternatively, the average height to base width ratio may be less than or equal to approximately 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, or 0.1:1.0.

[0063] At least some of the serrations or serrated ribs can have an average base width to top width ratio of about 1,000:1.0 to about 0.1:1.0. For example, the average base width to top width ratio can be about 0.1:1.0, 1.0:1.0, 2:1.0, 3:1.0, 4:1.0, 5:1.0, 6:1.0, 7:1.0, 8:1.0, 9:1.0, 10:1.0, 15:1.0, 20:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0 , 250:1.0, 300:1.0, 350:1.0, 450:1.0, 500:1.0, 550:1.0, 600:1.0, 650:1.0, 700:1.0, 750:1.0, 800:1.0, 850:1.0, 900:1.0, 950:1.0, or 1,000:1.0. Alternatively, the average base width to top width ratio is approximately 1,000:1.0, 950:1.0, 900:1.0, 850:1.0, 800:1.0, 750:1.0, 700:1.0, 650:1.0, 600:1.0, 550:1.0, 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, It may be 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, 20:1.0, 15:1.0, 10:1.0, 9:1.0, 8:1.0, 7:1.0, 6:1.0, 5:1.0, 4:1.0, 3:1.0, 2:1.0, 1.0:1.0, or 0.1:1.0 or less.

[0064] Backweb Thickness In some embodiments, the porous separator membrane can have a backweb thickness T-back of approximately 50 μm to approximately 1.0 mm. For example, the backweb thickness T-back can be approximately 50 μm, 75 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. In other exemplary embodiments, the backweb thickness T-back can be approximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less. In certain embodiments, very thin, flat backweb thicknesses of 50 μm or less, for example, thicknesses between approximately 10 μm and approximately 50 μm, are provided.

[0065] Envelope / Shape The separator 100 may be provided as a flat sheet, foil(s), wrap, sleeve, or as an envelope or pocket separator. An exemplary envelope separator may encase a positive electrode (a "positive electrode-encasing separator"), such that the separator has two inner sides facing the positive electrode and two outer sides facing the adjacent negative electrode. Alternatively, another exemplary envelope separator may encase a negative electrode (a "negative electrode-encasing separator"), such that the separator has two inner sides facing the negative electrode and two outer sides facing the adjacent positive electrode. In such an enveloped separator, the bottom edge 103 may be folded or may be a sealed fold edge. Additionally, the side edges 105a, 105b may be continuously or intermittently sealed seam edges. The edges may be bonded or sealed by adhesive, heat, ultrasonic welding, etc., or any combination thereof.

[0066] Certain exemplary separators may be processed to form hybrid envelopes. Hybrid envelopes may be provided by forming one or more slits or openings before, during, or after folding the separator sheet in half to form the envelope and bonding the edges of the separator sheet together. The length of the opening may 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 opening may 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 may 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 bottom edge. The corners of the envelope are preferably free of openings. The slits may be cut after the separator is folded and sealed to provide the envelope, or the slits may be formed before forming the porous membrane into the envelope.

[0067] Some other exemplary embodiments of separator assembly configurations include: ribs 104 facing the positive electrode; ribs 104 facing the negative electrode; a negative or positive electrode envelope; a negative or positive electrode sleeve, a negative or positive electrode hybrid envelope; both electrodes may be encased, sleeved, or any combination thereof.

[0068] composition In certain embodiments, the improved separator may include a porous membrane that may be comprised of: a natural or synthetic substrate; a processing plasticizer; a filler; a natural or synthetic rubber(s) or latex, and one or more other additives and / or coatings, and the like.

[0069] 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; cellulose fibers; and any combination thereof. In certain preferred embodiments, an exemplary separator may be a porous membrane made of a thermoplastic polymer. Exemplary thermoplastic polymers may include, in principle, any acid-resistant thermoplastic material suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers may include polyvinyls and polyolefins. In certain embodiments, polyvinyls may include, for example, polyvinyl chloride ("PVC"). In certain preferred embodiments, polyolefins may include, for example, polyethylene, polypropylene, ethylene-butene copolymers, and any combination thereof, preferably polyethylene. In certain embodiments, exemplary natural or synthetic rubbers may include, for example, latex, non-crosslinked or crosslinked rubber, crumb or ground rubber, and any combination thereof.

[0070] Polyolefin In certain embodiments, the porous membrane layer preferably comprises a polyolefin, specifically polyethylene. Preferably, the polyethylene is a high molecular weight polyethylene ("HMWPE") (e.g., a polyethylene having a molecular weight of at least 600,000). Even more preferably, the polyethylene is an ultra-high molecular weight polyethylene ("UHMWPE"). Exemplary UHMWPE may have 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 a viscometer and calculated according to the Margolie formula. Furthermore, exemplary UHMWPE may possess a standard load melt index of substantially zero (0) as measured as specified in ASTM D1238 (Condition E) using a 2,160 g standard load. Exemplary UHMWPE may also have a viscosity number, as determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130° C., 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.

[0071] rubber The novel separators disclosed herein may contain latex and / or rubber. As used herein, rubber 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 a variety of sources. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl rubber, and the like. Examples of suitable rubbers include polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and 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 rubbers may be crosslinked or non-crosslinked; in certain preferred embodiments, the rubbers are non-crosslinked. In certain embodiments, the rubbers may be blends of crosslinked and non-crosslinked rubbers.

[0072] plasticizer In certain embodiments, exemplary processing plasticizers may include processing oils, petroleum oils, paraffinic mineral oils, mineral oils, and any combination thereof.

[0073] Filler The separator may contain a filler having a high structural morphology. Exemplary fillers may include: silica, dry finely divided silica; precipitated silica; amorphous silica; very friable silica; alumina; talc; fish meal; fish bone meal; carbon; carbon black; and the like, and combinations thereof. In certain preferred embodiments, the filler is one or more silicas. High structural morphology refers to increased surface area. The filler may have a high surface area, for example, greater than 100 m / g, 110 m / g, 120 m / g, 130 m / g, 140 m / g, 150 m / g, 160 m / g, 170 m / g, 180 m / g, 190 m / g, 200 m / g, 210 m / g, 220 m / g, 230 m / g, 240 m / g, or 250 m / g. In some embodiments, the filler (e.g., silica) can have a high surface area of ​​100-300 m / g, 125-275 m / g, 150-250 m / g, or preferably 170-220 m / g. Surface area can be evaluated using a TriStar 3000™ for multipoint BET nitrogen surface area. High structural morphology allows the filler to retain more oil during the manufacturing process. For example, fillers with high structural morphology have high levels of oil absorption, e.g., greater than about 150 ml / 100 g, 175 ml / 100 g, 200 ml / 100 g, 225 ml / 100 g, 250 ml / 100 g, 275 ml / 100 g, 300 ml / 100 g, 325 ml / 100 g, or 350 ml / 100 g. In some embodiments, the filler (e.g., silica) may have an oil absorption of 200-500 ml / 100 g, 200-400 ml / 100 g, 225-375 ml / 100 g, 225-350 ml / 100 g, or 225-325 ml / 100 g, preferably 250-300 ml / 100 g. In some cases, a silica filler is used having an oil absorption of 266 ml / 100 g. Such silica filler has a water content of 5.1%, a BET surface area of ​​178 m / g, an average particle size of 23 μm, a 230-mesh sieve retention value of 0.1%, and a bulk density of 135 g / L.

[0074] Silica, which has a relatively high level of oil absorption and a relatively high level of affinity for plasticizer (e.g., mineral oil), is desirably dispersible in a mixture of polyolefin (e.g., polyethylene) and plasticizer when forming an exemplary lead-acid battery separator of the type shown herein. In the past, some separators have suffered from poor dispersibility caused by silica agglomeration when large amounts of silica were used to make such separators or membranes. In at least certain of the inventive separators shown and described herein, the polyolefin, e.g., polyethylene, forms a shish-kebab structure because there are fewer silica agglomerates or clumps that inhibit the molecular motion of the polyolefin upon cooling of the molten polyolefin. All of this contributes to improved ion permeability through the resulting separator membrane, and the formation of the shish-kebab structure or morphology means that a separator with a lower overall ER is produced while maintaining or even improving mechanical strength.

[0075] In some select embodiments, the filler (e.g., silica) has a particle size of 25 μm or less, or In some cases, the filler particles have an average particle size of 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm or less. In some cases, the average particle size of the filler particles is 15-25 μm. The particle size and / or surface area of ​​the silica filler contribute to the oil absorption of the silica filler. The silica particles in the final product or separator may be within the sizes listed above. However, the initial silica used as a raw material may occur as one or more clumps and / or agglomerates and may have a size of approximately 200 μm or more.

[0076] In some preferred embodiments, the silica used to make the separator of the present invention has an increased amount or number of specular silanol groups (specular hydroxyl groups) compared to silica fillers previously used to make lead-acid battery separators. For example, silica fillers that can be used according to certain preferred embodiments herein can be such silica fillers that have at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, or at least 35% more surface silanol and / or hydroxyl groups compared to known silica fillers used to make known polyolefin lead-acid battery separators.

[0077] The ratio of silanol groups (Si-OH) to silicon elements (Si), (Si-OH) / Si, can be measured, for example, as follows.

[0078] 1. Freeze-pulverize a polyolefin porous membrane (certain inventive membranes containing certain various oil-absorbing silicas according to the present invention) to prepare a powdered sample for solid-state nuclear magnetic resonance spectroscopy (29Si-NMR).

[0079] 2. Perform 29Si-NMR on the powdered sample and observe a spectrum containing Si spectral intensity directly bonded to hydroxyl groups (spectra: Q2 and Q3) and Si spectral intensity directly bonded only to oxygen atoms (spectra: Q4), where the molecular structure of each NMR peak spectrum can be expressed as follows: Q2:(SiO)2-Si * -(OH)2: has two hydroxyl groups Q3:(SiO)3-Si * -(OH): has one hydroxyl group Q4:(SiO)4-Si * : All Si bonds are SiO where Si * is identified as an element by NMR observation.

[0080] 3. The 29Si-NMR conditions used for the observation were as follows: ·Equipment: Bruker BioSpin Avance 500 ·Resonance frequency: 99.36MHz Sample size: 250mg NMR tube: diameter 7m Observation method: DD / MAS Pulse width: 45° Repeat time: 100 seconds Scans: 800 Magic Angle Rotation: 5,000Hz Chemical shift reference: -22.43 ppm (external reference) silicone rubber

[0081] 4. Numerically separate the spectral peaks and calculate the area ratios of the peaks belonging to Q2, Q3, and Q4. Then, based on these ratios, calculate the molar ratio of hydroxyl groups (-OH) directly bonded to Si. The conditions for numerical peak separation are as follows: Suitable range: -80 to -130 ppm Initial peak top: -93 ppm in Q2, -101 ppm in Q3, and -101 ppm in Q4 -111 ppm. Initial half-width: 400Hz for Q2, 350Hz for Q3, and 450Hz for Q4, respectively. Gaussian function ratio: 80% initially, 70-100% during fitting.

[0082] 5. Calculate the peak area ratios of Q2, Q3, and Q4 (totaling 100) based on the peaks obtained by fitting. The NMR peak areas correspond to the number of molecules of each silicate bond structure (thus, in the Q4 NMR peak, four Si-O-Si bonds exist in the silicate structure; in the Q3 NMR peak, three Si-O-Si bonds exist in the silicate structure, while one Si-OH bond exists; in the Q2 NMR peak, two Si-O-Si bonds exist in the silicate structure, while two Si-OH bonds exist). Therefore, multiply the number of hydroxyl groups (-OH) in Q2, Q3, and Q4 by 2, 1, and 0, respectively. Add up these three results. The sum represents the molar ratio of hydroxyl groups (-OH) directly bonded to Si.

[0083] In certain embodiments, the silica may range from about 21:100 to about 35:100, in some preferred embodiments from about 23:100 to about 31:100, in certain preferred embodiments from about 25:100 to about 29:100, and in other preferred embodiments, at least about 27:100 or more. 29 It may have a molar ratio of OH to Si groups as determined by Si-NMR.

[0084] In some select embodiments, the use of the fillers described above allows for the use of a greater proportion of process oil during the extrusion process. Because the porous structure in the separator is formed, in part, by the removal of oil after extrusion, a higher initial oil absorption results in a higher porosity or void volume. While process oil is an essential component of the extrusion process, the oil is a non-conductive component of the separator. Residual oil in the separator protects the separator from oxidation when in contact with the positive electrode. In conventional separator manufacturing, the exact amount of oil used during the processing process can be controlled. Generally speaking, conventional separators are manufactured using 50-70% process oil, in some embodiments, 55-65%, in some embodiments, 60-65%, and in some embodiments, about 62% by weight of process oil. Reducing the oil content below about 59% is known to cause burning due to increased friction against extruder components. However, increasing the oil content much beyond a predetermined amount can cause shrinkage during the drying stage, leading to dimensional instability. While previous attempts to increase the oil content resulted in pore shrinkage or condensation upon oil removal, separators prepared as disclosed herein exhibit minimal, if any, shrinkage and condensation upon oil removal. Thus, porosity can be increased without compromising pore size and dimensional stability, thereby reducing electrical resistance.

[0085] In certain selected embodiments, the use of the fillers described above allows for a reduced final oil concentration in the finished separator. Because oil is a non-conductor, reducing the oil content can increase the ionic conductivity of the separator and help lower the separator's ER. Therefore, separators with reduced final oil content can have increased efficiency. In certain selected embodiments, separators are provided that have a final processed oil content (by weight) of less than 20%, for example, between about 14% and 20%, and in some specific embodiments, less than 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, or 5%.

[0086] The filler may further reduce what is called the hydration layer of electrolyte ions and improve the transport of these ions across the membrane, thereby again lowering the overall electrical resistance or ER of the battery, e.g., supercharger battery, or system.

[0087] The filler(s) may contain various species (e.g., polar species, e.g., metals) that facilitate the flow of electrolyte and ions across the separator, which also leads to a reduction in overall electrical resistance when such separators are used in flooded batteries, e.g., high performance flooded batteries.

[0088] The filler (e.g., silica) may contain trace elements, such as sodium. The inventors have found that reducing sodium can increase cold cranking amps ("CCA"). For example, an exemplary separator with a 60% (by weight) reduction in sodium (compared to a typical commercially available separator) has a 10% increased CCA. Such a reduced sodium content in the finished separator sheet is 0.020 g / m 2 ~0.060g / m 2 It may be in the following range:

[0089] fragility In certain selected embodiments, the filler may be alumina, talc, silica, or a combination thereof. In some embodiments, the filler may be precipitated silica, and in some embodiments, the precipitated silica is amorphous silica. In some embodiments, it is preferable to use silica aggregates and / or agglomerates that allow for fine dispersion of the filler throughout the separator, thereby reducing tortuosity and electrical resistance. In certain preferred embodiments, the filler (e.g., silica) is characterized by a high level of friability. Good friability improves dispersion of the filler throughout the polymer during extrusion of the porous membrane, improving porosity and therefore overall ionic conductivity through the separator.

[0090] Friability can be measured as the ability, tendency, or propensity of silica particles or materials (aggregates or clumps) to break down into smaller, more disperse particles, pieces, or components. As shown on the left side of Figure 5, the novel silica is more friable (broken down into smaller pieces after 30 and 60 seconds of sonication) than standard silica. For example, the novel silica had a 50% by volume particle size of 24.90 μm at 0 seconds of sonication, 5.17 μm at 30 seconds, and 0.49 μm at 60 seconds. Thus, after 30 seconds of sonication, there was a greater than 50% size (diameter) reduction, and after 60 seconds, there was a greater than 75% reduction in the size (diameter) of the 50% by volume silica particles. Thus, one possible preferred definition of "high friability" could be a reduction in average size (diameter) of at least 50% in 30 seconds of sonication of silica particles (or in the treatment of a resin-silica mixture to form a membrane), and a reduction in average size (diameter) of at least 75% in 60 seconds of sonication. In at least certain embodiments, it may be preferable to use a more friable silica, and even more preferable to use a silica that is friable and multimodal, e.g., bimodal or trimodal, in its friability. Referring to Figure 5, the standard silica appears to be unimodal in its friability or particle size distribution, while the novel silica appears to be more friable and bimodal (two peaks) in 30 seconds of sonication and trimodal (three peaks) in 60 seconds of sonication. Such a friable and multimodal particle size silica(s) may impart improved membrane and separator properties.

[0091] The use of a filler having one or more of the above characteristics allows for the production of a separator with a higher final porosity. The separators disclosed herein may have a final porosity of greater than 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%. Porosity may be measured using a gas adsorption method. Porosity may be measured according to BS-TE-2060.

[0092] In some selected embodiments, the porous separator has a particle size of about 1 μm, 0.9 μm, 0 The porous membrane may have a higher proportion of larger pores while maintaining an average pore size of 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, or 0.1 μm or less.

[0093] According to at least one embodiment, the separator is made of polyethylene, such as ultra-high molecular weight polyethylene ("UHMWPE"), mixed with processing oil and fillers, as well as any desired additives. According to at least one other embodiment, the separator is made of ultra-high molecular weight polyethylene (UHMWPE) mixed with processing oil and talc. According to at least one other embodiment, the separator is made of UHMWPE mixed with processing oil and silica, such as precipitated silica, e.g., amorphous precipitated silica. The additives can then be applied to the separator via one or more of the techniques described above.

[0094] In addition to reduced electrical resistance and increased cold-cranking amps, the preferred separators are also designed to provide other benefits. For assembly, the separators are manufactured more efficiently because they pass through processing equipment more easily. To prevent short circuits during high-speed assembly and later in life, the separators have superior puncture strength and oxidation resistance compared to standard PE separators. Combined with reduced electrical resistance and increased cold-cranking amps, battery manufacturers are likely to see improved sustained electrical performance in batteries using these novel separators.

[0095] Additives / Surfactants In certain embodiments, exemplary separators may contain one or more performance-enhancing additives added to the separator or porous membrane. Performance-enhancing additives may be surfactants, wetting agents, colorants, antistatic additives, antimony suppression additives, UV-protective additives, antioxidants, and the like, as well as any combination thereof. In certain embodiments, the additives / surfactants may be ionic, cationic, anionic, or nonionic surfactants.

[0096] In certain embodiments described herein, reduced amounts of anionic or nonionic surfactants are added to the inventive porous membranes or separators. Due to the lower amounts of surfactant, desirable characteristics can include reduced total organic carbon ("TOC") and / or reduced volatile organic compounds ("VOCs").

[0097] 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. Certain suitable surfactants may have an HLB value of less than 6, preferably less than 3. The use of certain suitable surfactants in combination with the inventive separators described herein can lead to even further improved separators that, when used in lead-acid batteries, lead to reduced water loss, reduced antimony poisoning, improved cycling, reduced float current, reduced floating potential, etc., or any combination thereof for such lead-acid batteries. Suitable surfactants include surfactants such as salts of alkyl sulfates; alkylarylsulfonate salts; alkylphenol-alkylene oxide adducts; soaps; alkyl-naphthalene-sulfonate salts; one or more sulfosuccinates, such as anionic sulfosuccinates; dialkyl esters of sulfosuccinate salts; amino compounds (primary, secondary, tertiary, or quaternary amines); block copolymers of ethylene oxide and propylene oxide; various polyethylene oxides; and salts of mono- and dialkyl phosphate esters. Additives include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides, such as alkyl polyglycosides. These surfactants may include ethoxylated alkylaryl phosphate esters of fatty acids and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters of fatty acids, and sucrose esters.

[0098] In certain exemplary embodiments, TOC levels may be measured in mg per kg of finished separator. For example, such TOC levels may be measured by using a potassium persulfate solution to react with carbon in an ultraviolet ("UV") detection chamber. Such TOC levels preferably range from about 2,000 mg / kg or less, more preferably about 1,500 mg / kg or less, or even about 1,000 mg / kg or less.

[0099] In certain exemplary embodiments, the performance additive may be a wetting agent. The amount of wetting agent may be found by the following procedure. Cut eight 120mm x 120mm pieces evenly spaced across the width of the sample. Dry the samples in an air-circulating oven at 105°C-110°C (220°F-230°F) for at least 5 minutes, remove from the oven, and quickly weigh the sample to prevent moisture uptake (X1(g) = including oil). Place the sample pieces - gently fold them - into a Soxhlet extractor (or Soxtherm) and extract with vigorously boiling hexane for at least 60 minutes. Remove the sample pieces from the extractor and air dry them under a well-ventilated hood for 5 minutes. Dry the sample in an air-circulating oven at 105°C-110°C (220°F-230°F) for at least 5 minutes, remove from the oven and quickly weigh the sample to prevent moisture uptake (X2(g) = oil-free). Place the hexane-extracted sample back into the Soxhlet extractor (or Soxtherm) and extract with vigorously boiling isopropanol for at least 60-90 minutes. Decant the isopropanol completely from the Soxhlet into one or more round-bottom flasks. Evaporate the isopropanol under reduced pressure to accelerate evaporation. After complete removal of the isopropanol, place the flask(s) in an oven at 105°C for 10 minutes to remove any remaining traces of water. After cooling, transfer the residue to a 25 ml volumetric flask by dissolving and rinsing with several 5 ml portions of chloroform (Respelling: CCl4). Dilute the final solution in the volumetric flask to the 25 ml mark with chloroform. Fill a pair of cells, one with the sample solution and one with pure chloroform (Respelling: CCl4) for the background spectrum, according to the instructions of the particular IR spectrophotometer at the time of use. That's 4000~600cm -1 The scan is performed over a range of When the spectrum obtained shows no abnormalities, -1 The absorption band at is used to calculate the amount of wetting agent (g) (=X3) in the sample solution by automatic calculation performed by a computer-controlled spectrophotometer. X3 / X1 * 100 = % wetting agent in oil-containing sample (by weight) X3 / X2 * 100 = % wetting agent in oil-free sample (by weight) Particular embodiments may have a wetting agent content of approximately 0.60% or less. In certain embodiments, the additive may be represented by a compound of formula (I).

[0100]

number

[0101] During the ceremony: ·R is a linear or non-aromatic hydrocarbon radical having 10 to 4200, preferably 13 to 4200, carbon atoms, which may be interrupted by oxygen atoms.

[0102] ·R 1 =H,

[0103]

number

[0104] or

[0105]

number

[0106] Preferably, H, where k=1 or 2;

[0107] M is an alkali metal or alkaline earth metal ion, H + or NH4 + And this Here, all of the variable values ​​M are simultaneously H + does not mean; · n = 0 or 1; m = 0 or an integer between 10 and 1400; ·x=1 or 2.

[0108] 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. However, preferably, only one of the variables n and m is different from 0.

[0109] By non-aromatic hydrocarbon radical is meant a radical that does not contain or itself represents an aromatic group. The hydrocarbon radical may be interrupted by oxygen atoms (i.e., it may contain one or more ether groups).

[0110] R is preferably a straight-chain or branched aliphatic hydrocarbon radical, which may be interrupted by oxygen atoms. Saturated, non-bridged hydrocarbon radicals are highly preferred. However, as noted above, R may, in certain embodiments, contain an aromatic ring.

[0111] By using compounds of formula (I) in the production of battery separators, these separators can be effectively protected against oxidative breakdown.

[0112] Preferred are battery separators containing a compound according to formula (I), wherein: R is a hydrocarbon radical having 10 to 180, preferably 12 to 75, very preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20, very preferably 1 to 8 oxygen atoms, particularly preferably a hydrocarbon radical of the formula

[0113]

number

[0114] is a hydrocarbon radical of During the ceremony: ○ R 2 has 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 1 an alkyl radical having 4 to 20 carbon atoms, where R 2 is linear or non-linear may be linear, e.g., contain aromatic rings; p is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; q is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; Particularly preferred compounds are those in which the sum of p and q is 0 to 10, in particular 0 to 4; · n = 1; ·m=0.

[0115]

number

[0116] should be understood to include these compounds in which the sequence of the radicals in the brackets differs from that shown. For example, compounds according to the invention in which the radical in brackets is formed by alternating (OC2H4) and (OC3H6) groups are preferred.

[0117] R 2 linear or branched chain having 10 to 20, preferably 14 to 18 carbon atoms; Additives which are alkyl radicals have proven particularly advantageous. Preferably, OC2H4 represents OCH2CH2 and OCH(CH3)2 represents OC3H6 and / or OCH2CH2CH3.

[0118] As preferred additives, mention may be made in particular of alcohols (p=q=0; m=0), with primary alcohols being particularly preferred, and fatty alcohol ethoxylates (p=1-4, q=0), fatty alcohol propoxylates (p=0; q=1-4) and fatty alcohol alkoxylates (p=1-2; q=1-4) of primary alcohols being preferred. Fatty alcohol alkoxylates are obtainable, for example, by reacting the corresponding alcohols with ethylene oxide or propylene oxide.

[0119] Additives of the m=0 type, which are insoluble or simply poorly soluble in water and sulfuric acid, have proven to be particularly advantageous.

[0120] Also preferred are additives containing a compound according to formula (I), wherein: R is an alkane radical having 20 to 4200, preferably 50 to 750, very preferably 80 to 225, carbon atoms; M is an alkali metal or alkaline earth metal ion, H + or NH4 + , especially Alka Li metal ions, e.g., Li + , Na + and K. + , or H + where all of the variables M are simultaneously H + does not mean; ·n=0; · m = an integer between 10 and 1400; ·x=1 or 2.

[0121] Salt Additives In certain embodiments, suitable additives include, inter alia, polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers, the acid groups of which are, for example, preferred. The percentages refer to the number of acid groups. Poly(meth)acrylic acid present entirely in salt form is highly preferred. Suitable salts include those of Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium (NR4, where R is hydrogen or a carbon functional group). The poly(meth)acrylic acid may include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic 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 most preferably 1,000 to 4,000 g / mol. w Poly(meth)acrylic acid polymers and polyacrylic acids having the formula The molecular weight of the copolymers is confirmed by measuring the viscosity of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution (Fikentscher's constant).

[0122] Copolymers of (meth)acrylic acid are also suitable, especially those containing ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and / or ethylhexyl acrylate as comonomers other than (meth)acrylic acid. Preferred are copolymers containing at least 40% by weight, preferably at least 80% by weight, of (meth)acrylic acid monomer; the percentages are based on the acid form of the monomer or polymer.

[0123] Alkali metal and alkaline earth metal hydroxides, such as potassium hydroxide and especially sodium hydroxide, are particularly suitable for neutralizing polyacrylic acid polymers and copolymers. Separator-enhancing coatings and / or additives may also include, for example, metal alkoxides, where the metal may be, by way of example only (and not intended to be limiting), Zn, Na, or Al, by way of example only, sodium ethoxide.

[0124] In some embodiments, the porous polyolefin membrane may include a coating on one or both sides of the 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 may, for example, reduce the overcharge voltage of the battery system, thereby reducing grid corrosion and extending battery life, and may also prevent dryout and / or water loss.

[0125] ratio In certain selected embodiments, membranes can be prepared by combining, by weight, about 5-15% polymer, in some cases about 10% polymer (e.g., polyethylene), about 10-75% filler (e.g., silica), in some cases about 30% filler, and about 10-85% processing oil, in some cases about 60% processing oil. In other embodiments, the filler content is reduced and the oil content is higher, e.g., about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or greater than 70% by weight. The filler:polymer ratio (by weight) can be approximately (or can be approximately between these specified ranges), for example, 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. The filler: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 with respect to feasibility and desired separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, torsion, etc.

[0126] 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 porous 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 certain cases, the porous polymer layer can be a homogeneous mixture of 8-100% by volume polyolefin, 0-40% by volume plasticizer, and 0-92% by volume inert filler material. A preferred plasticizer is petroleum. Plasticizers are useful for imparting porosity to battery separators because they are the easiest component to remove from polymer-filler-plasticizer compositions by solvent extraction and drying.

[0127] In certain embodiments, the porous membranes disclosed herein may contain 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 sources. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and 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; in certain preferred embodiments, the rubber is non-crosslinked. In certain embodiments, the rubber may be a blend of crosslinked and non-crosslinked rubber. The rubber may be present in the separator in an amount that is at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight relative to the final separator weight (weight of the polyolefin separator sheet or layer containing the rubber and / or latex). In certain embodiments, the rubber may be present in an amount of approximately 1-6%, approximately 3-6%, approximately 3%, or approximately 6% by weight. The porous membrane may have a filler to polymer and rubber (filler:polymer and rubber) weight ratio of approximately 2.6:1.0. The amounts of rubber, filler, oil, and polymer are all balanced with respect to feasibility and desired separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, torsion, etc.

[0128] Porous membranes made according to the present invention, including polyethylene and a filler (e.g., silica), typically have residual oil; in some embodiments, such residual oil is about 0.5% to up to about 40% of the total weight of the separator membrane (in some cases, about 10-40% of the total weight of the separator membrane, and in some cases, about 20-40% of the total weight). In certain select embodiments herein, some to all of the residual oil in the separator may be replaced by the addition of an additional performance-enhancing additive, such as a surfactant, e.g., a surfactant having a hydrophilic-lipophilic balance ("HLB") of less than 6, or, for example, a nonionic surfactant. For example, the performance-enhancing additive, e.g., a surfactant, e.g., a nonionic surfactant, may partially or completely replace the residual oil in the separator membrane by comprising up to 0.5% of the total weight of the porous separator membrane up to the amount of residual oil (e.g., up to 20%, or 30%, or even 40%).

[0129] Conductive layer A conductive layer may be disposed on the exemplary battery separator 100. The conductive layer may preferably be adapted to contact the battery's positive electrode (not shown). The conductive layer may be for providing a new current path to and from the positive electrode (not shown). The conductive layer may be limited The conductive layer may be made of any conductive material, including, but not limited to, lead, gold, antimony, arsenic, zinc, barium, beryllium, lithium, magnesium, nickel, aluminum, silver, tin, and alloys thereof, or carbon fiber, graphite, carbon nanotubes, buckminsterfullerenes (or buckyballs), and combinations thereof. The carbon nanotubes or buckyballs may be dispersed in a medium containing a binder and applied to the battery separator. The conductive layer may be made of any conductive material that is more corrosion-resistant than the positive conductor, thereby allowing the conductive layer to function as the positive conductor when the conductive performance of the positive conductor deteriorates. The conductive layer may be a lead-based alloy containing 0.8% to 1.17% tin and greater than zero (0) to 0.015% silver. The conductive layer may be a lead-based alloy containing 0.02% to 0.06% calcium, 0.3% to 3% tin, and 0.01% to 0.05% silver. The conductive layer may be fabricated in any form, including but not limited to, a strip, a screen, a foil, a thread, a wire, a coating, or the like, or a combination thereof. The conductive layer may be of any thickness, for example, approximately 3 μm thick. The conductive layer may be applied to the battery separator by any means, including but not limited to, adhesive, heat melting, painting, or the like. The conductive layer may be as described in U.S. Pat. No. 9,564,623, the entirety of which is incorporated herein by reference.

[0130] Nucleating Additives In certain embodiments, the separator may contain a nucleating additive and / or a performance-enhancing additive in the form of a coating. The nucleating additive may preferably be stable in the battery electrolyte and may further be dispersed within the electrolyte.

[0131] Exemplary forms of the nucleating additive and / or coating may be or contain carbon, e.g., carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, Ketjenblack, carbon fiber, carbon filament, carbon nanotubes, open cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, and combinations thereof. In addition to these many forms of carbon, the nucleating additive and / or coating may also contain barium sulfate (BaSO), either alone or in combination with carbon. It may contain or may contain either one of them.

[0132] The nucleation coating may be applied to the finished separator by such means as slurry coating, slot die coating, spray coating, curtain coating, ink jet printing, screen printing, or by vacuum deposition or chemical vapor deposition ("CVD"). The additive and / or coating may also be provided as carbon paper, either woven or nonwoven fabric, and may be disposed between and in intimate contact with the separator and electrode(s).

[0133] The nucleating additive and / or coating may be present within the separator or on one or both of the electrode-facing surfaces of the separator. Typically, the nucleating additive coating or layer will be present only on the negative electrode-facing surface. However, it may also be present on the positive electrode-facing surface or on both surfaces.

[0134] In certain embodiments, the nucleating additive may be added to the substrate extrusion mix and extruded with the separator or co-extruded as a layer on the separator. When included in the extrusion mix, the nucleating additive may replace some of the silica filler by as much as 5% to 75% by weight. For example, the nucleating additive may be approximately 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or approximately 75% by weight. In other exemplary embodiments, the nucleating additive The additive may be approximately 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or approximately 5% by weight or less.

[0135] manufacturing In some embodiments, exemplary porous membranes can be produced by mixing the components in an extruder. For example, about 30% by weight of filler, including about 10% by weight of UHMWPE, and about 60% processing oil can be mixed in an extruder. Exemplary porous membranes can be produced by passing the components through a heated extruder, passing the extrudate produced by the extruder through a die, and passing it through a nip formed by two heated press or calender stacks or rolls to form a continuous web. A significant amount of processing oil from the web can be extracted using a solvent, followed by drying to remove the solvent. The web can then be cut into lanes of a predetermined width and then wound into a roll. In addition, the press or calender roll can be provided with various groove patterns to impart ribs, grooves, textured areas, embossments, etc., substantially as described herein.

[0136] Rubber manufacturing In some embodiments, exemplary porous membranes may be produced by mixing the components in an extruder. For example, about 5-15% by weight of polymer (e.g., polyethylene), about 10-75% by weight of filler (e.g., silica), about 1-50% by weight of rubber and / or latex, and about 10-85% by weight of processing oil may be mixed in the extruder. Exemplary porous membranes may be produced by passing the components through a heated extruder, passing the extrudate through a die, and passing it through a nip formed by two heated press or calender stacks or rolls to form a continuous web. A substantial amount of the processing oil from the web may be extracted using a solvent. The web may then be dried, slit into lanes of a predetermined width, and then wound into a roll. Additionally, the press or calender roll may be provided with various groove patterns to impart ribs, grooves, textured areas, embossments, etc., substantially as described herein. 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, and the like.

[0137] In addition to being added to the extruder components, certain embodiments incorporate the rubber into the porous 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 to form a film of this material on the mirror surface of the exemplary porous membrane. For better wetting of this layer, known wetting agents may be added to the slurry used in lead-acid batteries. In certain embodiments, the slurry may also contain one or more performance-enhancing additives described herein. After drying, a porous layer and / or film is formed on the mirror surface of the separator, adhering very well to the porous membrane and increasing electrical resistance only slightly, if at all. After being added, the rubber may be further compressed using either a mechanical press or a calender stack or rolls. 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 into lanes.

[0138] A further embodiment of the present invention includes depositing the rubber onto the membrane by impregnation and drying.

[0139] Manufactured with performance-enhancing additives In certain embodiments, performance-enhancing additive(s) (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, etc., as well as any combination thereof) may be mixed with the other components in the extruder. A porous membrane according to the present disclosure may then be extruded into a sheet or web shape and finished in substantially the same manner as described above.

[0140] In certain embodiments, in addition to or as an alternative to addition in the extruder, the additive(s) may be applied, for example, to the separator porous membrane when it is completed (e.g., after the bulk of the processing oil is extracted, and before or after the introduction of the rubber). 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 non-thermally stable additives and additives that are soluble in the solvent used to extract the processing oil. Particularly suitable solvents for the additives according to the present invention are low-molecular-weight alcohols, such as methanol and ethanol, and mixtures of these alcohols with water. Application may be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or both. Application may also be carried out during extraction of the pore-forming agent (e.g., processing oil) in a solvent bath. In certain selected embodiments, some of the performance-enhancing additives, such as surfactant coatings or performance-enhancing additives (or both) added to the extruder before the separator is made, may combine with the antimony in the battery system and may deactivate it, and / or form compounds with it, and / or cause it to drip into the battery mud rest, and / or prevent it from depositing on the negative electrode. The surfactant or additive may also be added to the electrolyte, glass mat, battery case, adhesive paper, adhesive mat, etc., or combinations thereof.

[0141] 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 / m 2 , 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 until Additives may be present at density or add-on levels. Additives may be present at density levels between 0.5 and 15 g / m 2 , 0.5~1 0g / 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 , 3.0~10.0g / m 2 , 3.5 to 10.0 g / m 2 , 4.0~10.0g / m 2 , 4.5 to 10.0 g / m 2 , 5.0~10.0g / m 2 , 5 .5~10.0g / m 2 , 6.0~10.0g / m 2 , 6.5 to 10.0 g / m 2 , 7.0 ~10.0g / m 2 , 7.5 to 10.0 g / m 2 , 4.5 to 7.5 g / m 2 , 5.0~10 .5g / m 2 , 5.0~11.0g / m 2 , 5.0~12.0g / m 2 , 5.0~15.0 g / m 2 , 5.0~16.0g / m 2 , 5.0~17.0g / m 2 , 5.0~18.0g / m 2 , 5.0~19.0g / m 2 , 5.0~20.0g / m 2 , 5.0~21.0g / m2 , 5.0~22.0g / m 2 , 5.0~23.0g / m 2 , 5.0~24.0g / m 2 ,Also is 5.0 to 25.0 g / m 2 Density or add-on levels between .

[0142] Application may also be performed by immersing the battery separator in the additive or a solution of the additive (solvent bath addition) and removing the solvent as needed (e.g., by drying). In this way, application of the additive may be combined with extraction, which is often applied, for example, in membrane production. Other preferred methods include spraying the mirrored surface with the additive, die coating, roller coating, or curtain coating one or more additives onto the mirrored surface of the separator.

[0143] In certain embodiments described herein, reduced amounts of ionic, cationic, anionic, or nonionic surfactants are added to the separators of the present invention. In such cases, desirable characteristics may include reduced total organic carbon and / or reduced volatile organic compounds (due to the lower amount of surfactant) that may produce desirable separators of the present invention according to such embodiments.

[0144] Combination with fibrous mat In certain embodiments, exemplary separators according to the present disclosure may be combined with another layer (laminated or otherwise), such as a fibrous layer or fibrous mat, having improved wicking and / or electrolyte wetting or retention properties. The fibrous mat may be a woven fabric, nonwoven fabric, fleece, mesh, netting, single layer, multi-layer (where each layer may have the same, similar, or different characteristics as the other layers), and may be composed of glass fibers, or synthetic fibers, fleece, or fibers made from synthetic fibers or a mixture of synthetic fibers or glass and synthetic fibers or paper, or any combination thereof.

[0145] In certain embodiments, the fibrous mat (laminated or otherwise) may be used as a carrier for additional materials. The additive materials may include, for example, rubber and / or latex, optionally silica, water, and / or one or more performance-enhancing additives, such as the various additives described herein, or any combination thereof. By way of example, the additional materials may then be coated onto one or more surfaces of the fibrous mat to form a film, or may be delivered in the form of a slurry that can be immersed and impregnated into the fibrous mat.

[0146] When a fibrous layer is present, the porous membrane preferably has a larger surface area than the fibrous layer. Therefore, when the porous membrane and fibrous layer are combined, the fibrous layer does not completely cover the porous layer. Preferably, at least two opposing edge regions of the membrane layer remain uncovered so that the edges are prepared for heat sealing to facilitate the optional formation of pockets, envelopes, etc. Such a fibrous mat may have a thickness of at least 100 μm, and in some embodiments, 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 separator to be subsequently laminated may be cut into pieces. In one particular embodiment, the fibrous mat is laminated to the ribbed mirror surface of the porous membrane. In certain embodiments, handling and / or assembly advantages are provided to battery manufacturers because the improved separators described herein can be supplied in roll and / or cut strip form. Also, as previously mentioned, the improved separators can be stand-alone separator sheets or layers without the addition of one or more fibrous mats or the like.

[0147] When the fibrous mat is laminated to the porous membrane, they may be adhered together by adhesives, heat, ultrasonic welding, compression, etc., or any combination thereof. The fibrous mat may also be a PAM or NAM bearing mat.

[0148] basic weight In certain select embodiments, exemplary separators have a porosity of 1000 psi (g / m 2 Measured in units of The separator may be characterized by its basis weight (also referred to as area weight). Exemplary separators may exhibit reduced basis weights. For example, exemplary separators may exhibit a reduced basis weight of approximately 90 g / m 2 ~approximately 140g / m 2In certain selected embodiments, The basis weight is approximately 90 g / m 2 , 100g / m 2 , 110g / m 2 , 120g / m 2 , 130g / m 2 , or 140 g / m 2 In other embodiments, the basis weight may be 140 g / m 2 , 130g / m 2 , 120g / m 2 , 110g / m 2 , 100g / m 2 , 9 0g / m 2 Exemplary separators are preferably Approximately 90g / m 2 ~approximately 130g / m 2 Less than or equal to 90 g / m 2 ~approximately 120g / m 2 It has the following basis weight:

[0149] Basis weight is simply determined by weighing a sample and then dividing that value by the area of ​​the sample. For example, take a 1.0 m x 1.0 m sample and weigh it. The area is calculated without regard to ribs, grooves, embossments, etc. As an example, a 1.0 m x 1.0 m sample of ribbed separator has the same area as a 1.0 m x 1.0 m sample of flat separator.

[0150] Electrical resistance In certain select embodiments, the disclosed separators exhibit reduced electrical resistance. For example, exemplary separators exhibit a resistance of approximately 20 mΩ·cm. 2 ~approximately 200mΩ cm 2 In certain selected embodiments, the electrical resistance ("ER") may be: The separator has a resistance of approximately 20 mΩ·cm 2 , 30 mΩ·cm 2 , 40 mΩ·cm2 , 50mΩ ·cm 2 , 60 mΩ·cm 2 , 80mΩ·cm 2 , 100mΩ·cm 2 , 120 mΩ·cm 2 , 140 mΩ·cm 2 , 160mΩ·cm 2 , 180mΩ·cm 2 , or 200 mΩ·c m 2 In other selected embodiments, the ER may be about 200 mΩ·c m 2 , 180mΩ·cm 2 , 160mΩ·cm 2 , 140 mΩ·cm 2 , 120 mΩ·cm 2 , 100mΩ·cm 2 , 80mΩ·cm 2 , 60 mΩ·cm 2 , 50 mΩ·cm 2 , 40 mΩ·cm 2 , 30 mΩ·cm 2 , or 20 mΩ·cm 2 However, ER further increased to 20 mΩ·cm 2 In various embodiments, the present invention The separators described herein exhibit a reduction in ER of about 20% or more compared to known separators of the same thickness. For example, known separators have an ER of 60 mΩ cm. 2 has an ER value of so that the separator according to the present invention has a resistance of about 48 mΩ·cm at the same thickness. 2 Not yet The resulting product will have an ER value of 0.05.

[0151] To test a sample separator for ER test evaluation according to the present invention, it must first be prepared. To do so, the sample separator is preferably immersed in a bath of demineralized water, the water is then boiled, and the separator is then removed after 10 minutes in the boiling demineralized water bath. After removal, excess water is removed from the separator, which is then placed in a bath of sulfuric acid having a specific gravity of 1.280 at 27°C ± 1°C. The separator is immersed in the sulfuric acid bath for 20 minutes. The separator is then ready to be tested for electrical resistance.

[0152] Oxidative stability In certain select embodiments, exemplary separators may be characterized by improved, higher oxidation resistance. Oxidation resistance is measured by elongation of a sample separator specimen in the width direction after prolonged exposure to lead-acid battery electrolyte. For example, exemplary separators may have an elongation at 40 hours of approximately 150% or more, 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more. In certain embodiments, exemplary separators may have a preferred oxidation resistance or elongation at 40 hours of approximately 200% or more.

[0153] To test the sample for oxidation resistance, an exemplary separator sample specimen 400 is cut into a shape as generally depicted in Figure 6A. The sample 400 is then placed in a sample holder as generally shown in Figure 6B.

[0154] The first set of samples is tested dry at a time of zero (0) hours and at a % stretch to failure. The stretch is based on a 50 mm distance measured from points A and B in Figure 6A. For example, if points A and B are stretched to a distance of 300%, the final distance between A and B will be 150 mm.

[0155] The elongation test is designed to simulate long-term exposure to the electrolyte in a cycling battery over a shortened period of time. The sample 400 is first completely submerged in isopropanol, drained, and then submerged in water for 1-2 seconds. The sample is then submerged in the electrolyte solution. The solution is prepared by adding 360 ml of 1.28 specific gravity sulfuric acid, 35 ml of 1.84 specific gravity sulfuric acid, and then 105 ml of 35% hydrogen peroxide, in that order. The solution is maintained at 80°C, and the sample is immersed in the solution for an extended period of time. The sample may be tested for elongation at regular intervals, such as 20 hours, 40 hours, 60 hours, and 80 hours. To test at these intervals, the sample 400 is removed from the 80°C electrolyte bath and placed under a stream of lukewarm water until the acid is removed. The elongation can then be tested.

[0156] According to at least selected embodiments, the present disclosure or invention is directed to improved battery separators, low ER or high conductivity separators, improved lead-acid batteries, e.g., flooded lead-acid batteries, high conductivity batteries, and / or improved vehicles including such batteries, and / or methods of making or using such separators or batteries, and / or combinations thereof. According to at least certain embodiments, the present disclosure or invention is directed to improved lead-acid batteries incorporating the improved separators and exhibiting increased conductivity.

[0157] conclusion According to selected embodiments, an improved or new battery separator includes a porous membrane having a backweb with a plurality of ribs extending from at least a portion of the backweb. The porous membrane may include a composition of a polymer, a filler, at least one performance-enhancing additive, a plasticizer, and optionally a rubber. The separator may have an acid-leachable total organic carbon ("TOC") of approximately 2,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, preferably approximately 1,500 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber, and more preferably approximately 1,000 mg or less per kg of battery separator as measured by a potassium persulfate solution reacting with carbon in an ultraviolet detection chamber.

[0158] Selected embodiment refinements may provide at least some of the ribs as positive electrode ribs extending from the positive electrode facing the surface of the porous membrane, and at least some of the ribs as negative electrode ribs extending from the negative electrode facing the surface of the porous membrane, or embodiments may include both positive and negative electrode ribs. Either or both of the positive and negative electrode ribs may extend uniformly from the first lateral edge to the second lateral edge, or none may extend uniformly from the first lateral edge to the second lateral edge. Either or both of the positive and negative electrode ribs may extend uniformly from the top edge to the bottom edge, or none may extend uniformly from the top edge to the bottom edge. Either or both of the positive and negative electrode ribs may be designed and optimized to reduce dendrite formation and growth.

[0159] In certain exemplary separators, any positive and / or negative ribs The set may be any one of the following: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, slanted ribs, linear ribs, ribs extending longitudinally in a substantially machine direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending transversely in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag sawtooth ribs, broken discontinuous zigzag sawtooth ribs, grooves, channels, textured regions, embossments, dimples, cylinders, miniature cylinders, porous, non-porous, intersecting ribs, miniature ribs, intersecting miniature ribs, and combinations thereof.

[0160] In select exemplary separators, any positive and / or negative rib set may be a broken rib, with the rib having a distinct end point contained within the separator edge and disconnected from any other rib. The broken rib may be defined by an angular orientation that improves acid mixing in the battery, particularly during battery operation, with the separator disposed therein and positioned parallel to the battery's start and stop motion. The angular orientation may be defined relative to the separator's MD and may be an angle between zero degrees (0°) and less than 180 degrees (180°), or between 180 degrees (180°) and less than 360 degrees (360°). The angular orientation of the ribs may vary across multiple ribs. In certain select embodiments, exemplary separators may have multiple rib sets, with each rib set having a different or the same angular orientation compared to the other rib sets. In other exemplary separators, the positive and / or negative electrode ribs may have an angular orientation that is between zero degrees (0°) and three hundred sixty degrees (360°).

[0161] In select embodiments, the positive electrode ribs may have a rib height of approximately 50 μm to approximately 2.0 mm. Additionally, at least some of the positive electrode ribs may have a base width of approximately 300 μm to approximately 750 μm. In some exemplary embodiments, at least some of the positive electrode ribs may have a second base width of approximately 400 μm to approximately 500 μm. When at least some of the positive electrode ribs and / or negative electrode ribs are substantially straight and substantially parallel to each other, they may have a spacing length of approximately 50 μm to approximately 20 mm.

[0162] In certain exemplary embodiments, the height of the negative electrode rib may be approximately 5.0% or less to approximately 100% or more of the height of the positive electrode rib. For example, a battery separator may have negative electrode ribs with a height range of approximately 5.0 μm to approximately 2.0 mm. Exemplary negative electrode ribs may have a base width of approximately 5 μm to approximately 500 μm.

[0163] In selected exemplary embodiments, aspects of the present invention provide a separator or porous membrane having a composition that may include any or more of the following: 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, cellulose fiber, rubber, and combinations thereof.

[0164] The improvement of the present invention provides that the rubber can be any one or more of the following: crosslinked rubber, non-crosslinked rubber, cured rubber, non-cured rubber, natural rubber, latex, synthetic rubber, and combinations thereof. Another improvement of the present invention provides that the rubber can be any one or more of the following: methyl rubber, polybutadiene, one or more chloroprene rubbers, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, silicone rubber, copolymer rubber, and combinations thereof. Additionally, the copolymer rubber can be any one or more of the following: styrene / butadiene rubber, acrylonitrile rubber, methyl acrylate ... The rubber may be any one or more of: ethylene / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), ethylene / vinyl acetate rubber, and combinations thereof.

[0165] In select embodiments, the rubber may be present in an amount that is about 1% to about 6% by weight, preferably about 3% by weight, preferably about 6% by weight, and more preferably about 3% to about 6% by weight. The rubber may be mixed with other substrates of the separator or coated onto at least a portion of one or more surfaces of the separator or porous membrane. When coated, the rubber may be applied as a liquid slurry and dried.

[0166] Exemplary embodiments of the present invention may possess a filler that may be any one or more of the following: silica, dry finely divided silica; precipitated silica; amorphous silica; alumina; talc; fish meal, fish bone meal, and combinations thereof. Further, the silica may be in the range of about 21:100 to 35:100, about 23:100 to about 31:100, about 25:100 to about 29:100, or alternatively at least about 27:100 or greater. 29 It may have a molar ratio of OH:Si groups as determined by Si-NMR.

[0167] Exemplary fillers of the present invention may provide exemplary fillers with high structural morphology. The improvements of the present invention include: having an average particle size of 5 μm or less; 2 / g Exemplary fillers may be provided that are characterized by one of the group consisting of: having a surface area; having an oil absorption rate of at least 150 ml / 100 mg; and combinations thereof.

[0168] The separator or porous membrane may have a filler to polymer (filler:polymer) weight ratio of about 2.0:1.0 to about 4.0:1.0, for example, about 2.0:1.0; alternatively, about 2.6:1.0; also alternatively, such as about 3.5:1.0; and a filler to combination of filler and rubber (filler:polymer and rubber) by weight of about 2.0:1.0 to about 3.0:1.0, for example, 2.6:1.0.

[0169] Exemplary porous membranes can have a backweb thickness of from about 100 μm to about 400 μm, preferably from about 100 μm to about 250 μm, preferably from about 100 μm to about 200 μm, preferably from about 100 μm to about 150 μm, and most preferably from about 100 μm to about 100 μm.

[0170] Exemplary separators according to the present disclosure may have an overall thickness of from about 100 μm to about 1.0 mm, preferably from about 100 μm to about 850 μm, preferably from about 100 μm to about 650 μm, preferably from about 100 μm to about 450 μm, preferably from about 100 μm to about 250 μm, and most preferably from about 100 μm to about 150 μm.

[0171] Another aspect of the present invention may provide at least one performance-enhancing additive, which may be one or more of the following: surfactants, wetting agents, colorants, antistatic additives, antimony suppression additives, UV-protection additives, antioxidants, and combinations thereof. The improvement provides that exemplary surfactants are one or more of the following: nonionic surfactants, ionic surfactants, anionic surfactants, cationic surfactants, and combinations thereof. Furthermore, exemplary performance-enhancing additives may possess lithium ions, aluminum ions, or both.

[0172] Exemplary embodiments are at least approximately 0.5 g / m 2 ~approximately 6g / m 2 , alternatively, approximately 0.5 g / m 2 ~approximately 3g / m 2 The surfactant may be provided in an amount of The agent may, for example, be coated on at least a portion of the porous membrane or separator, impregnated within at least a portion of the porous membrane or separator, or mixed with the polymer and filler prior to extrusion of the porous membrane.

[0173] Another aspect of the present invention provides a porous membrane or separator comprising a processing plasticizer, which may be, for example, processing oil, petroleum oil, paraffinic mineral oil, mineral oil, and combinations thereof. The plasticizer is typically added to the mixture of polymer, filler, and optional performance-enhancing additives prior to extrusion of the porous membrane. After extrusion, a portion of the plasticizer may be extracted by known means.

[0174] In some select embodiments, the separator further comprises a fibrous mat that may be attached or adhered to the separator in some manner or simply disposed adjacent thereto. The mat may be composed of any one or more of the following: glass fiber, synthetic fiber, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, or a combination thereof. The mat may also be a nonwoven fabric, a woven fabric, a fleece, a net, or a combination thereof.

[0175] Exemplary separators may exhibit improved performance parameters, such as lower electrical resistance ("ER"), compared to conventional separators. For example, the ER may be approximately 65 mΩ·cm. 2 Less than or equal to 50 mΩ·cm, preferably 2 Less than or equal to approximately 35 mΩ·c, most preferably m 2 It may be the following:

[0176] Exemplary separators may include a conductive layer on one or both of the positive and negative electrode sides of the separator. The separator may also have an oxidation resistance of approximately 200% or greater at 40 hours. Furthermore, separators may take on various shapes and / or configurations. For example, exemplary separators may be any one of the following: cut pieces, pockets, sleeves, wraps, envelopes, hybrid envelopes, S-woven separators, or include side folds.

[0177]

[0010] Embodiments of the present invention also provide batteries using separators substantially as described herein. For example, the battery may be a lead-acid battery, such as a flat-plate battery, a flooded lead-acid battery, an advanced flooded lead-acid battery ("EFB"), a deep-cycle battery, a gel battery, an absorbent glass mat ("AGM") battery, a tubular battery, an inverter battery, a vehicle battery, a start-stop light ignition ("SLI") vehicle battery, an idle-stop ("ISS") vehicle battery, a car battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric vehicle battery, an electric rickshaw battery, an electric bicycle battery, an uninterruptible power supply ("UPS") battery, or a solar or wind or other renewable energy storage system battery. Exemplary batteries may be used at a partial state of charge with a possible depth of discharge of between approximately 1% and approximately 99%, possibly between approximately 1% and approximately 50%, and additionally between approximately 50% and approximately 99%. Batteries may be utilized in driving, stationary, energy storage system applications; renewable energy storage system applications; continuous power supply applications; energy storage system applications, backup power applications, cycling applications, and combinations thereof.

[0178] Other embodiments may include systems including a battery substantially as described herein. Such systems may include energy storage systems; renewable energy storage systems; continuous power supplies; energy storage systems, backup power systems, and combinations thereof. Such systems may be used in vehicles, such as automobiles, trucks, motorcycles, all-terrain vehicles, forklifts, golf carts, hybrid vehicles, hybrid electric vehicles, and the like. The batteries may further include batteries for electric vehicles, electric cars, idle-stop (“ISS”) cars, water containers, batteries for electric rickshaws, electric tricycles, and electric bicycles.

[0179] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of certain aspects of the claims; any compositions and methods that are functionally equivalent are intended to be within the scope of the claims. Various modifications of the compositions and methods, in addition to those shown and described herein, are intended to be within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of such compositions and method steps are also intended to be within the scope of the appended claims, even if not specifically recited. Thus, although combinations of steps, elements, components, or components may be explicitly recited herein or below, other combinations of steps, elements, components, and components are also included, even if not explicitly recited. The term "comprising" and variations thereof, as used herein, is used synonymously with the term "including" and variations thereof, and is an open, non-limiting term. Although the terms "comprising" and "including" are used herein to describe various embodiments, the terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, which are also disclosed. In addition to those in the examples, or where otherwise stated, all numbers expressing ingredients, reaction conditions, and the like used in the specification and claims should be understood at a minimum and should be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the doctrine of equivalents to the claims.

[0180] According to at least selected embodiments, aspects or objects disclosed or provided herein are new or improved separators, battery separators, super-flooded battery separators, batteries, cells, and / or methods of making and / or using such separators, battery separators, super-flooded battery separators, cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved battery separators for super-flooded batteries. Also disclosed herein are methods, systems, and battery separators having reduced ER, improved puncture strength, improved separator CMD puncture stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for super-flooded batteries having reduced ER, improved puncture strength, improved separator CMD puncture stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, or any combination thereof. According to at least certain embodiments, separators are provided that include or exhibit reduced ER, improved puncture strength, improved separator CMD puncture stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, separators are provided for flat plate batteries, tubular batteries, battery applications for vehicle SLI and HEV ISS applications, deep cycle applications, batteries for golf cars or golf carts and electric rickshaws, batteries operating at partial state of charge ("PSOC"), inverter batteries; and storage batteries for renewable energy sources, and any combination thereof.

[0181] The present invention may be embodied in other forms without departing from its spirit or essential characteristics, and therefore, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the invention. Components that can be used to perform the method are disclosed. These and other components are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these components are specifically contemplated and described herein for all methods and systems, even if specific reference to each of their various individual and collective combinations may not be expressly disclosed. This applies to all aspects of this application, including, but not limited to, the steps in the disclosed methods. Thus, where there are various additional steps that can be performed, it is understood that these additional steps may each be performed by any specific embodiment or combination of embodiments of the disclosed methods.

[0182] The above detailed descriptions of structures and methods have been presented for purposes of illustration only. Examples are used to disclose exemplary embodiments, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems 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, and many modifications and variations are possible in light of the above teachings. Features described herein may be combined in any combination. Method steps 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 when they have structural elements that do not differ from the literal language of the claims, or when they include equivalent structural elements that have insubstantial differences from the literal language of the claims.

[0183] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of certain aspects of the claims. Any compositions and methods that are functionally equivalent are intended to be within the scope of the claims. Various modifications of the compositions and methods, in addition to those shown and described herein, are intended to be within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of such compositions and method steps are also intended to be within the scope of the appended claims, even if not specifically recited. Thus, although combinations of steps, elements, components, or components may be explicitly referred to herein or below, other combinations of steps, elements, components, and components are also included, even if not explicitly recited.

[0184] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms a separate embodiment. It will be further understood that each of the endpoints of a range is significant both in relation to the other endpoint, and independently of the other endpoint. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances when said event or circumstance occurs and instances when said event or circumstance does not occur.

[0185] Throughout this specification and the claims, the word "comprises" " and variations of such words, such as "comprising" and "comprises," mean "including but not limited to," and are not intended to exclude, for example, other additives, components, integers, or steps. The terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, which are also disclosed. "Exemplary" or "for example" means "an example of" and is not intended to convey an indication of a preferred or ideal embodiment. Similarly, "such as" is used for descriptive or illustrative purposes, not in a limiting sense.

[0186] Except as otherwise stated, all numbers expressing geometric shapes, dimensions, and the like used in the specification and claims should be understood as a minimum and should be construed in light of the number of significant digits and ordinary rounding approaches, and not as an attempt to limit the doctrine of equivalents to the claims.

[0187] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. All publications cited herein and the materials to which they refer are specifically incorporated by reference.

[0188] Additionally, the invention illustratively disclosed herein may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. 1. A battery separator comprising a porous membrane, The separator has a density of 0.020 to 0.060 g / m ２ sodium, the porous membrane is filled with silica as a filler, The filler has an average particle size of more than 0 μm and 5 μm or less, and a surface area of ​​100 m ２ / g or more and 300 m 2 / g or less, an oil absorption rate of 150 ml / 100 mg or more and 500 ml / 100 mg or less, and a combination thereof.

2. The battery separator of claim 1, wherein the porous membrane comprises one or more ribs selected from the group consisting of solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, slanted ribs, linear ribs, ribs extending longitudinally in the lengthwise direction of the porous membrane, ribs extending laterally in the widthwise direction of the porous membrane, ribs extending transversely in the widthwise direction of the separator, discrete dentations, toothed ribs, sawtooth ribs, crested, crested ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag sawtooth ribs, broken discontinuous zigzag sawtooth ribs, grooves, channels, textured regions, embossments, dimples, cylinders, small cylinders, porous, non-porous, crossing ribs, small ribs, crossing small ribs, and combinations thereof.

3. A battery separator as described in claim 1, wherein the porous membrane contains 1% to 50% by weight of rubber and / or latex.

4. 10. The battery separator of claim 1, comprising a conductive layer on one or both of the positive and negative electrode sides.

5. 5. The battery separator of claim 4, wherein said conductive layer is applied to said battery separator by means including adhesive, heat melting, and painting.

6. The battery separator of claim 4, wherein the conductive layer comprises lead, gold, antimony, arsenic, zinc, barium, beryllium, lithium, magnesium, nickel, aluminum, silver, tin, and combinations thereof, or carbon fiber, graphite, carbon nanotubes, buckminsterfullerenes (or buckyballs), or combinations thereof.

7. A battery separator as described in claim 4, wherein the conductive layer is in any form including a strip, screen, foil, thread, wire, or coating.

8. The battery separator of claim 4, wherein the battery separator is one of a sleeve, a wrap, an envelope, a hybrid envelope, an S-woven separator, or a separator with side folds.

9. A positive electrode and a negative electrode adjacent to the positive electrode; The separator according to any one of claims 1 to 8, at least a portion of which is disposed between the positive electrode and the negative electrode; an electrolyte immersing at least a portion of the positive electrode, at least a portion of the negative electrode, and at least a portion of the separator; Lead-acid batteries operating in a partial state of charge, including:

10. 10. The lead-acid battery of claim 9, wherein the battery operates at a depth of discharge between 50% and 99%, or between 1% and 50%.

11. A lead-acid battery further comprising a mat adjacent to at least one of the positive electrode, the negative electrode, and the separator, 10. The lead-acid battery of claim 9, wherein the mat optionally 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.

12. A lead-acid battery further comprising a mat adjacent to at least one of the positive electrode, the negative electrode, and the separator, 10. The lead-acid battery of claim 9, wherein the mat optionally comprises one of the group consisting of a nonwoven fabric, a woven fabric, a mesh, a fleece, a net, and combinations thereof.

13. The battery In driving, stationary and energy storage system applications, In renewable energy storage system applications, In continuous power supply applications, 10. The lead-acid battery of claim 9, operated in one of the group consisting of: in an energy storage system application, in a backup power supply application, in a cycling application, and combinations thereof.

14. The lead-acid battery of claim 9, wherein the battery is selected from the group consisting of flat plate batteries, flooded lead acid batteries, advanced flooded lead acid batteries ("EFB"), deep cycle batteries, gel batteries, absorbent glass mat ("AGM") batteries, tubular batteries, inverter batteries, vehicle batteries, start-stop ("SLI") vehicle batteries, idle-stop ("ISS") vehicle batteries, automobile batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, water container batteries, electric tricycle batteries, electric rickshaw batteries, and electric bicycle batteries.

15. A positive electrode and a negative electrode adjacent to the positive electrode; a battery separator according to any one of claims 4 to 8, at least a portion of which is disposed between the positive electrode and the negative electrode; an electrolyte immersing at least a portion of the positive electrode, at least a portion of the negative electrode, and at least a portion of the separator; Lead-acid batteries operating in a partial state of charge, including:

16. The battery In driving, stationary and energy storage system applications, In renewable energy storage system applications, In continuous power supply applications, Operate in one of the group consisting of: in an energy storage system application, in a backup power supply application, in a cycling application, and combinations thereof; 16. The lead-acid battery of claim 15.

17. the battery is selected from the group consisting of flat plate batteries, flooded lead acid batteries, advanced flooded lead acid batteries ("EFB"), deep cycle batteries, gel batteries, absorbent glass mat ("AGM") batteries, tubular batteries, inverter batteries, vehicle batteries, start-stop ("SLI") vehicle batteries, idle-stop ("ISS") vehicle batteries, car batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, water container batteries, electric tricycle batteries, electric rickshaw batteries, and electric bicycle batteries; 16. The lead-acid battery of claim 15.

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