Improved lead acid battery separators and batteries containing the same

Abstract

To provide separators that mitigate or prevent issues such as stratification and deterioration of battery performance or battery life, and lead acid batteries containing the separators.SOLUTION: Disclosed in one embodiment is a battery separator comprising a substrate that may be polymeric and porous. The substrate may have ribs, protrusions, or ribs and protrusions on one or both faces or surfaces thereof. On at least one surface or face of the substrate, a material layer may be formed. The material layer may contain a material with an oil absorption value equal to or greater than 15 g oil / 100 g of material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to new or improved separators for various lead-acid batteries and / or systems. Additionally, exemplary embodiments disclosed herein are directed to new or improved battery separators, battery cells incorporating same, batteries incorporating same, systems incorporating same, and / or methods of making and / or using same, and / or the like, and / or combinations thereof. [Background technology]

[0002] Lead-acid batteries are a very economical solution to energy storage and have been the preferred energy source for starting vehicles for about 100 years. For most of this century, the lead-acid battery's primary role was to easily start the engine several times a day and to provide power for emergency lights in the event that the vehicle became inoperable due to engine malfunction. To start a vehicle, a lead-acid battery is typically discharged to less than 5% of its full capacity and then quickly recharged to 100% by the running engine. Thus, traditional lead-acid batteries used in automotive applications typically operated at 100% charge.

[0003] To improve fuel economy and reduce emissions, manufacturers have designed vehicles called idle stop-start (“ISS”) vehicles, resulting in their engines being turned off more frequently. ISS vehicle engines turn off when the vehicle is stopped and automatically restart when the vehicle is moving again. Typically, the engine restarts when the brake pedal is released. In addition to restarting the engine, the ISS vehicle battery needs to provide energy for the vehicle's accessories when the engine is off. Exemplary accessories may be HVAC systems, heated seats, radios, lights, and the like. When these vehicles are operated in heavy traffic, such as in cities or other densely populated areas, lead-acid batteries typically operate at a partial state of charge (“PSoC”) and may never (or rarely) reach a full charge. PSoC exists when the battery operates at less than 100% charge and typically survives this state through multiple charge-discharge cycles without reaching 100% charge. This operation at PSoC has highlighted various weaknesses in the state of the art in lead-acid battery technology. Thus, currently there is still an unmet need in lead acid battery technology.

[0004] Referring to FIG. 1 , a typical lead-acid battery 50 includes a positive terminal 51 and a negative terminal 53. The terminals 51, 53 are typically located on the top or sides of the battery 50. Within the battery, an electrode / separator array 50a includes alternating positive and negative electrodes 52, 54, and a porous or microporous separator 100 disposed and interleaved between each positive electrode 52 and negative electrode 54. The positive terminal 51 is in electrical communication with the positive electrode 52. Similarly, the negative terminal 53 is in electrical communication with the negative electrode 54. While the separators 100 are shown as leaf or cut-off separators 100, they may alternatively be formed as positive electrode envelopes (i.e., enveloping the positive electrode), negative electrode envelopes (i.e., enveloping the negative electrode), hybrid envelopes, pockets, sleeves, wraps, and / or the like, and / or combinations thereof. Typically, the separator may comprise a microporous silica-filled polyethylene (PE) membrane separator or backweb (102 or 202) with a backweb 102 or 202 and ribs or protrusions 104. 102n or 202n denotes the negative side or face of the backweb, and 102p or 202p denotes the positive side or face of the backweb.

[0005] A typical positive electrode 52 consists primarily of lead dioxide (PbO2), usually a positive electrode active material ("PAM"). A typical negative electrode 54 is comprised primarily of lead (Pb) and typically comprises a current-carrying grid doped with a negative electrode active material ("NAM"). Both M and NAM contribute to increased functionality of the electrodes. The positive and negative grids may include alloys containing at least one of antimony (Sb), calcium (Ca), tin (Sn), selenium (Se), and / or the like, or combinations thereof.

[0006] An aqueous electrolyte solution 56 substantially immerses the electrodes 52, 54 and separator 100. In lead-acid batteries, the electrolyte 56 solution serves as both the electrolyte and the reactant and is typically a solution of water and sulfuric acid (H2SO4). The electrolyte solution typically has a pH of about 1.280 (1280 Kg / m 3) and has an optimum specific gravity of approximately 1.215 (1215 kg / m 3 ) ~ approx. 1.300 (1300Kg / m 3 ) range.

[0007] The purpose of the separator is to physically separate and insulate the electrodes from mutual electrical conduction, which would short-circuit the battery, while maintaining ionic conduction between the electrodes via the electrolyte necessary for the battery's electrochemical reactions. Therefore, the separator must be electrically non-conductive (e.g., other than carbon coating one side) and porous enough to electrically separate the electrodes and allow ionic conduction (e.g., via the electrolyte filling the pores). If the separator is too porous or has pores that are too large, dendrites may form large enough to bridge the gap between the electrodes, shorting the battery. Extremely large pores may also allow direct physical contact between the electrodes. Because the electrolyte also serves as a reactant, the separator must also allow sufficient acid to contact and interact with the electrodes.

[0008] The reaction at the lead dioxide (PbO2) positive (+) electrode (the "cathode half-reaction") donates electrons to become a cathode. This cathode half-reaction during discharge at the lead dioxide (PbO2) positive (+) electrode produces lead sulfate (PbSO4) and water (HO), as shown in Equation 1:

[0009] PbO2+SO4 -2 +4H + +2e - <-> PbSO4+2H2O (Eq. 1) · PbO2 is a solid lead dioxide positive (+) electrode; SO4 -2 is aqueous; 4H + is aqueous; 2e - is present in the solid lead dioxide (PbO2) positive (+) electrode; PbSO4 is a solid precipitate in aqueous electrolytes; and ·H2O is the liquid in aqueous electrolytes.

[0010] The cathode half-reaction is reversible during battery charging.

[0011] The negative half-reaction ("negative half-reaction") at the lead (Pb) negative (-) electrode donates positive ions, becoming negative. During discharge, the negative half-reaction produces lead sulfate (PbSO4) and negative ions (e - ) is generated and shown in Equation 2 below:

[0012] Pb+SO4 -2 <-> PbSO4+2e - (Formula 2) During the ceremony: Pb is a solid lead negative electrode; SO4 -2 is aqueous; PbSO4 is a solid precipitate in aqueous electrolytes; and 2e - is a lead (Pb) negative (-) electrode.

[0013] The negative half-reaction is reversible during battery charging.

[0014] Together, these half-reactions add up to the overall chemical reaction of a lead-acid battery, as shown in Equation 3 below.

[0015] Pb+ PbO2+2H2SO4<-> 2PbSO4+2H2O (Formula 3) During the ceremony: Pb is a solid lead negative electrode; ·PbO2 is a solid positive (+) electrode; ·H2SO4 is a liquid in aqueous electrolyte; PbSO4 is a solid precipitate in aqueous electrolytes; and ·H2O is the liquid in aqueous electrolytes.

[0016] The overall chemical reactions are reversible during battery charging. For each of the above reactions, discharging causes a shift from left to right, and charging causes a shift from right to left. During a discharge cycle, both the positive (+) and negative (-) electrodes are at least partially converted to lead sulfate (PbSO4), and the electrolyte loses most of its sulfuric acid (H2SO4) and becomes mostly water. As shown in FIG. 2A, a fully discharged battery cell includes two electrodes 52, 54, one of lead sulfate and the other of dilute sulfuric acid, with a separator 100 disposed between the electrodes 52, 54. As shown in FIG. 2B, a fully charged battery cell includes a lead dioxide electrode 52, a lead electrode 54, and sulfuric acid electrolyte, with a separator 100 disposed between the electrodes 52, 54.

[0017] A particular weakness of typical lead-acid batteries operating in PSoC is the generation of lead sulfate (PbSO4) during the discharge cycle. As shown in the equations above (see Equations 1, 2, and 3), both electrodes consume sulfuric acid from the electrolyte, leaving behind an electrolyte with a lower specific gravity. At the same time, the electrodes convert, at least partially, to lead sulfate. Lead sulfate becomes richer than lead, resulting in active material (e.g., NAM and PAM) expansion. If this active material is unconstrained, it will shed over time, shortening the battery's lifespan. If the active material is constrained, it will maintain contact with the current-carrying grid and readily convert from lead sulfate to lead. Overall, the active material is essentially unsupported in typical flooded batteries. In sealed lead-acid ("VRLA") batteries, an absorbent glass mat ("AGM") separator provides more support by providing full contact with the active material. While providing support, the AGM separator is infinitely compressible and does not fully tolerate the expansion of the active material during discharge. Although the AGM separator may prevent shedding, the active material may lose electrical connection with the current collector and remain in a sulfated state.

[0018] Another particular weakness of typical lead-acid batteries operating in PSoC is electrolyte stratification. During the charge cycle, the electrodes convert from a sulfated state, producing sulfuric acid (H2SO4). The acid produced is more concentrated than the rest of the electrolyte, which is dilute sulfuric acid. In addition, sulfuric acid is denser than water. Therefore, most of the acid produced sinks to the bottom of the cell / battery and eventually stratifies with the more concentrated acid at the bottom of the electrolyte. Stratification shortens battery life, degrades battery electrical performance, and can cause battery management systems to issue false signals about charging the battery.

[0019] Yet another particular weakness of typical lead-acid batteries operating in PSoC relates to the fact that the battery is typically located in the engine compartment of a vehicle. For various reasons, vehicle manufacturers are continually optimizing the use of volume within the vehicle. As such, engine compartments are becoming smaller and more crowded, thereby reducing airflow through the engine compartment. With reduced airflow and operation in a high temperature environment, a typical lead-acid battery can reach temperatures in excess of 80°C. The positive electrode is subject to oxidative chemistry on the surface that can degrade the typical polyethylene separator. Furthermore, high temperatures only accelerate the oxidation reactions by many orders of magnitude, further accelerating the degradation of polyethylene separators. Summary of the Invention [Problem to be solved by the invention]

[0020] A need still exists to at least partially address the above-mentioned problems or issues related to the known weaknesses of typical lead-acid batteries operating in PSoC. The present application and the inventors provide a novel battery separator, as described herein, that preferably provides sufficient support for active material expansion, reduces, mitigates, or eliminates stratification, and would be highly oxidation-resistant. The same novel separator would preferably maintain the current advantages of existing separators, such as polyethylene separators, with low ionic resistance, excellent puncture resistance, envelope properties, and remain highly cost-effective. At the time of filing this application, the inventors are unaware of any battery separator that can provide all of these properties as described herein or in the embodiments described herein. Therefore, the present invention preferably aims to satisfy at least these and other heretofore largely unmet needs. [Means for solving the problem]

[0021] At least for certain applications or batteries, details of one or more exemplary embodiments, aspects, or objects of the present invention provide a battery separator having at least a variable overall thickness, such as an overall thickness that varies as a function of pressure applied to the separator. Other features, objects, and advantages of the present invention provide reduced battery failure, increased battery cycle life, and / or improved performance. More particularly, there remains a need to provide a separator that can accommodate various electrode spacings during at least one of battery production and / or post-production use.

[0022] Details of one or more exemplary embodiments, aspects, or objects are set forth in the specification and claims set forth below. Other features, objects, and advantages will become apparent from the specification and claims set forth below. According to one or more selected embodiments, aspects, or objects, the present disclosure or invention addresses at least the problems, challenges, or needs enumerated herein, and in some cases surprisingly and unexpectedly provides a solution that exceeds the need and expectations.

[0023] According to at least certain example embodiments, objects, or aspects, the present disclosure or invention may provide new or improved separators, cells, batteries, systems, methods of manufacture, uses, and / or applications of such new or improved separators, cells, batteries, and / or systems that overcome at least the aforementioned problems. For example, at least certain example embodiments, objects, or aspects provide a battery with separators that can conform to electrodes by providing a battery with separators having various thicknesses with various spacings therebetween.

[0024] In at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention provides a separator whose components and physical attributes and characteristics synergistically combine in surprising and unexpected ways to address a previously unmet need in the lead-acid battery industry with an improved battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a battery that utilizes the separator described herein to address a previously unmet need in the lead-acid battery industry with an improved lead-acid battery separator in a surprising and unexpected way. In certain preferred exemplary embodiments, the present disclosure or invention provides an improved system that utilizes the inventive lead-acid batteries that utilize the inventive separators described herein in a surprising and unexpected way. The present invention provides a system that uses the batteries described herein to address a previously unmet need in the lead acid battery industry.

[0025] According to at least certain embodiments, the present disclosure or invention relates to new or improved separators, cells, batteries, systems, and / or methods of manufacturing and / or uses and / or applications of such new separators, cells, batteries, and / or systems. According to at least certain embodiments, the present disclosure or invention relates to new or improved lead-acid batteries; flooded lead-acid batteries; enhanced flooded lead-acid batteries ("EFB"); flat plate batteries; tubular batteries; deep cycle batteries; batteries operating at partial state of charge ("PSoC"); sealed lead-acid batteries ("VRLA"); gel batteries; absorbed glass mat ("AGM") batteries; inverter batteries; stationary batteries; batteries used in transit; energy storage for power generation such as steam turbine generators, coal- and / or gas-fired power plants, and / or nuclear power plants; energy storage for power generation such as from solar, wind, hydroelectric, or other alternative and / or renewable energy sources; general energy storage batteries; uninterruptible power supplies. The present disclosure or invention is directed to vehicle batteries such as power supply ("UPS") batteries; batteries with high cold cranking amps ("CCA") requirements; starting, lighting, and ignition ("SLI") vehicle batteries, idle start-stop ("ISS") vehicle batteries, marine batteries, car batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart (also known as golf cars) batteries, hybrid electric vehicle ("HEV") batteries, electric vehicle batteries, e-rickshaw batteries, e-tricycle batteries, e-bike batteries, electric scooter batteries; and / or the like; and / or combinations thereof. According to selected embodiments, the present disclosure or invention relates to battery separators for use in systems or vehicles incorporating such batteries. According to at least certain aspects, the present disclosure or invention relates to improved methods of making and / or using such improved separators, cells, batteries, systems, and / or the like.

[0026] In one aspect, a battery separator is described that comprises, consists of, or consists essentially of: (1) a polymeric substrate; and (2) a material layer provided on at least one side of the polymeric substrate. In some preferred embodiments, a material layer may be provided on two or more sides of the polymeric substrate.

[0027] In a preferred embodiment, with respect to the polymeric substrate, the polymeric substrate is a flexible polymeric substrate. In some embodiments, the oil content of the polymeric substrate is 1-20%, 1-10%, or 1-5%. The polymeric substrate may be a nonwoven or woven polymeric substrate. The polymeric substrate may be a sheet or an envelope.

[0028] In some preferred embodiments, the polymer substrate is a porous polymer membrane having a positive electrode surface and a negative electrode surface, each of which optionally includes ribs, protrusions, or both ribs and protrusions. The porous polymer membrane may have pores with an average pore size of less than about 1 micron. The porous polymer membrane may be perforated, or may be microporous, nanoporous, macroporous, or mesoporous. The porous polymer membrane may comprise a polyolefin, including at least one of polyethylene, polypropylene, and blends or copolymers thereof. The porous polymer membrane may further comprise a filler in addition to the polyolefin.

[0029] In embodiments where ribs are present, the ribs may be at least one selected from continuous ribs, discontinuous ribs, longitudinally extending ribs, laterally extending ribs, diagonally extending ribs, integral ribs, non-integral ribs, and mini-ribs. In some embodiments, ribs, protrusions, or both ribs and protrusions may not be present on one or more outer edges of the membrane. In such embodiments, if ribs or protrusions are present on one or more outer edges of the membrane, they may be mini-ribs or mini-protrusions. The mini-ribs or mini-protrusions may have a height of at most 100 microns to 250 microns above the surface of the polymeric porous membrane.

[0030] The thickness of the polymeric substrate may range from 50 to 500 microns. In embodiments where ribs, protrusions, or both ribs and protrusions are formed on the surface of the substrate, the thickness of the backweb (not including the rib height) is 50 to 500 microns. In some embodiments, the combined thickness of the polymeric substrate and material layer may be from 125 microns to 4 mm.

[0031] With respect to the material layer, the material layer may be provided on the positive electrode surface, the negative electrode surface, or both the positive and negative electrode surfaces of the polymeric porous membrane. The material layer may be provided on a side or surface that has ribs, protrusions, or both ribs and protrusions, or the material layer may be provided on a side or surface that has no ribs, no protrusions, or neither ribs nor protrusions. In embodiments where the material layer is provided on a side or surface that has ribs, protrusions, or both ribs and protrusions, the material layer may be provided between at least two ribs, between two protrusions, or between a rib and a protrusion. However, in embodiments where mini-ribs or mini-protrusions are present at the outer edge of the membrane, it is preferred that the material layer not be provided between these mini-ribs, between these mini-protrusions, or between the mini-ribs and the mini-protrusions.

[0032] In embodiments in which a layer of material is provided between two ribs, two protrusions, or a rib and a protrusion, the layer of material may partially fill, completely fill, or overfill the area between the two ribs, two protrusions, or rib and a protrusion.

[0033] In some preferred embodiments, the material layer comprises, consists of, or consists essentially of a material having an oil absorbency of greater than 15g oil / 100g material. The oil absorbency of the material may be greater than 25g oil / 100g material, 25g oil / 100g material to 100g oil / 100g material, 25g oil / 100g material to 200g oil / 100g material, or 25g oil / 100g material to 300g oil / 100g material.

[0034] The material may be at least one selected from the group consisting of silica, precipitated silica, fumed silica, talc, diatomaceous earth, polysulfone, polyester, PVC, and combinations thereof. In some embodiments, the material may be organic or inorganic particles that are at least one of hydrophilic, acidophilic, and acid-stable. In some embodiments, the material may include particles having different average diameters.

[0035] In some embodiments, the material layer may comprise, consist of, or consist essentially of the above materials and a binder. The binder may be present in an amount of less than 50% and, in some cases, in an amount of 1-20%. The binder may be soluble, partially soluble, or insoluble in battery acid, such as H2SO4.

[0036] In some embodiments, the material layer may further comprise, consist of, or consist essentially of at least one additional material. The additional material need not necessarily have the oil absorption properties of the material, but can. In some preferred embodiments, the additional material is at least one selected from the group consisting of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, any other battery performance enhancing additive, and combinations thereof.

[0037] In some embodiments, the material or material layer has a density of 0.1 to 3.5 g / cm 3 Range of volume It may have a density.

[0038] In some embodiments, an additional layer is provided on the material layer. The additional material may comprise, consist of, or consist essentially of at least one selected from the group consisting of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, a metal sulfate salt, any other battery performance enhancing additive, and combinations thereof. The additional layer may comprise, consist of, or consist essentially of a binder or other additive, or combinations thereof.

[0039] In another aspect, lead-acid batteries are described herein, which may include flooded lead-acid batteries or sealed lead-acid batteries. In some embodiments, the lead-acid batteries may include: (1) a negative plate; (2) a positive plate; (3) an acid-containing electrolyte; and (4) a battery separator as described herein disposed between at least one negative plate and at least one positive plate. The lead-acid batteries may be cylindrical or prismatic cell types.

[0040] A battery separator material layer may be formed between the polymer substrate and the positive plate, between the polymer substrate and the negative plate, or between the polymer substrate and both the positive and negative plates.

[0041] In some embodiments, an additional layer may be formed between the polymer substrate and the negative and / or positive plates. The additional material may comprise, consist of, or consist essentially of at least one of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, a metal sulfate salt, any other battery performance enhancing additive, and combinations thereof.

[0042] The lead-acid batteries described herein above, or the battery separators provided therein, may exhibit or do at least one, at least two, at least three, or all of the following properties: (1) immobilizing at least a portion of the acid-containing electrolyte; (2) not being infinitely compressible; (3) improving oxidation resistance allowing for thinner, more porous base or substrate materials; or (4) constraining the active material (NAM or PAM) in at least one of the positive or negative plates.

[0043] In another aspect, a sealed lead acid battery (VRLA) is described herein. The VRLA improvement described herein is the replacement of at least one absorbent glass mat (AGM) with a battery separator described herein. The VRLA battery may be a cylindrical cell type or a prismatic cell type.

[0044] A battery separator material layer may be formed between the polymer substrate and the positive plate of the VRLA battery, between the polymer substrate and the negative plate of the VRLA battery, or between the polymer substrate and both the positive and negative plates of the VRLA battery.

[0045] In some embodiments, an additional layer may be formed between the polymer substrate and the negative and / or positive plates. The additional material may comprise, consist of, or consist essentially of at least one of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, any other battery performance enhancing additive, and combinations thereof.

[0046] A VRLA battery or separator therein may exhibit at least one, at least two, or all of the following properties: (1) immobilizing at least a portion of the acid-containing electrolyte; (2) not being infinitely compressible; and (3) constraining the active material (NAM or PAM) in at least one of the positive or negative plates. [Brief explanation of the drawings]

[0047] [Figure 1] FIG. 1 is a schematic cutaway side view of a typical lead-acid battery comprising a plurality of interleaved positive (+) and negative (-) electrodes with separators interposed therebetween. [Figure 2A] FIG. 2A is a schematic diagram of a typical lead-acid battery cell in a substantially discharged state. [Figure 2B] FIG. 2B is a schematic diagram of a lead-acid battery cell substantially in a charged state. [Figure 3A] FIG. 3A is a plan view of an exemplary separator having a first surface or face having a plurality of ribs longitudinally disposed thereon and extending therefrom, substantially parallel to the machine direction. [Figure 3B]FIG. 3B shows a plan view of the separator shown in FIG. 3A with a second surface or face opposite the first surface or face having a plurality of optional anode cross ribs 106 disposed laterally thereon and extending therefrom and substantially parallel to the width direction. [Figure 4A] FIG. 4A is an end view of a typical separator with major ribs and a flat backweb. [Figure 4B] FIG. 4B is an end view of a typical separator with main ribs and anode cross ribs 106 on opposite sides. [Figure 5A] FIG. 5A is an end view of a typical electrode / separator assembly in a fully charged state. [Figure 5B] FIG. 5B is an end view of a typical electrode / separator assembly in a fully discharged state. [Figure 5C] FIG. 5C is a cross-sectional detail taken along line AA of FIG. 5A. [Figure 6A] FIG. 6A is a schematic end view of an exemplary embodiment of the invention including positive ribs. [Figure 6B] FIG. 6B is a schematic end view of an exemplary embodiment of the invention with a flat porous membrane without ribs. [Figure 6C] Figure 6C is an end view of an electrode / separator assembly comprising the separator of Figure 6A in either a charged or discharged state. The material layer is labeled 210 in these figures. [Figure 6D] FIG. 6D is a cross-sectional view. [Figure 7A] FIG. 7A is a cross-sectional view taken along line BB in FIG. 6C. [Figure 7B] FIG. 7B is a side detail view similar to that of FIG. 7B, with an exemplary separator of the present invention having negative cross ribs. [Figure 8A] 8A is a plan view of an exemplary embodiment comprising a flat-back web separator having no ribs, no protrusions, or no ribs and protrusions. If ribs or protrusions are present in the side regions, they are mini-ribs or mini-protrusions. [Figure 8B] Figure 8B is an end view of an exemplary embodiment as an envelope separator. The backweb is 202 and the side areas without ribs and protrusions are 212. 200 denotes the separator. 214 denotes the sealing area of ​​the formed envelope shown in Figures 8B and 8C. [Figure 8C] Figure 8C is an end view of an exemplary embodiment as an envelope separator. The backweb is 202 and the side areas without ribs or protrusions are 212. 200 denotes the separator. 214 denotes the sealed area of ​​the formed envelope shown in Figures 8B and 8C. [Figure 9] FIG. 9 is a schematic end view of an exemplary embodiment of the invention including positive ribs. DETAILED DESCRIPTION OF THE INVENTION

[0048] Described herein are improved battery separators for lead-acid batteries, including flooded lead-acid batteries or sealed lead-acid (VRLA) batteries. The battery separators described herein may replace one or more absorbent glass mats (AGMs) in VRLA batteries. The improved battery separators described herein can be used to There are many advantages. One advantage is that the battery separators described herein are not infinitely compressible like typical AGMs. Another advantage of the battery separators described herein is their ability to constrain liquid electrolyte, which may help prevent stratification, which can adversely affect battery life and performance, as described herein above. Another advantage that the battery separators described herein may exhibit is their ability to constrain the anode active material (NAM), the cathode active material (PAM), or both the NAM and PAM, which may swell, grow, and / or expand during battery operation. These advantages, among others, are realized by the improved battery separators disclosed herein.

[0049] Battery Separator While the structure of the battery separator described herein is not particularly limited, in a preferred embodiment, the battery separator may have the following structure: (1) a substrate and (2) a material layer formed on at least one surface or face of the substrate. In other embodiments, another layer (3) may be formed as part of the structure. The substrate particles, material layer, and other optional layers are described in more detail above and below.

[0050] (1) Base material The substrate of the battery separator is not particularly limited and may be polymeric or non-polymeric. The substrate of the battery separator may be porous or non-porous. However, in a preferred embodiment, the substrate is flexible, polymeric, and porous or perforated. For example, many commercially available battery separators sold by DARAMIC® may be used as the polymer substrate of the battery separator described herein. For example, Daramic® HiCharge™, Daramic® HP™, DuraLife®, Daramic® HD™, or Daramic® HD Plus™, Darak®, XCHARge™, HiCharge™, Daramic® EFS™, or Daramic® IND CL™ may be used. The substrate may be formed by a variety of methods, including, but not limited to, methods typical for producing nonwovens, including extrusion methods, casting methods, and spunbond nonwoven methods, or methods typical for producing woven fabrics.

[0051] The composition of the polymeric substrate is not particularly limited. The polymeric substrate may have a composition including at least one of a polymer, a thermoplastic polymer, polyvinyl chloride ("PVC"), a phenolic resin, natural or synthetic rubber, synthetic wood pulp, lignin, glass fiber, synthetic fiber, cellulose fiber, and / or combinations thereof. Natural or synthetic rubber may include rubber, latex, natural rubber, synthetic rubber, crosslinked or uncrosslinked natural or synthetic rubber, cured or uncured rubber, crumb rubber or ground rubber, polyisoprene, 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, as well as copolymer rubbers such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene / propylene rubber ("EPM" and "EPDM"), and ethylene-vinyl acetate rubber, and / or combinations thereof.

[0052] In some aspects of the present invention, the polymer-based composition may further comprise a filler. In some embodiments, the filler is selected from the group consisting of silica, precipitated silica, amorphous silica, highly brittle silica, alumina, talc, fish meal, fish bone meal, barium sulfate (BaSO), carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, ketjen black, carbon fiber, carbon filament, carbon nanotube, At least one of open-cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerenes ("buckyballs"), carbon aqueous suspension, graphite flakes, carbon oxide, and / or combinations thereof.

[0053] In some embodiments, the polymeric substrate composition may further include residual process oil from the manufacture of the substrate. One advantage of the battery separators described herein is the ability to reduce the process oil content in the substrate to less than 20%, less than 15%, less than 10%, or less than 5%. For example, the process oil content may be reduced to 1% or less, 2% or less, 3% or less, 4% or less, 5% or less, 6% or less, 7% or less, 8% or less, 9% or less, 10% or less, 11% or less, 12% or less, 13% or less, 14% or less, 15% or less, 16% or less, 17% or less, 18% or less, 19% or less, or even 20% or less. Traditionally, a significant amount of process oil is left behind to improve, among other things, oxidation resistance. However, by adding a material layer on at least one surface of the polymeric substrate in the battery separators described herein, the amount of residual process oil in the substrate can be reduced, with less concern about the oxidation resistance of the substrate. Reducing the amount of process oil can have the favorable effect of increasing the ionic conductivity of the substrate and / or lowering the electrical resistance across the substrate. Thus, the ability to have lower amounts of residual process oil in the substrate can significantly result in improved separator performance. While the ability to reduce the process oil content of the substrate is an advantage made possible by the improved battery separator structures described herein, battery separator embodiments in which the substrate has a process oil content greater than 20% are also feasible and have other advantages.

[0054] In some embodiments, one or more surfaces or faces of the substrate may include ribs, protrusions, or both ribs and protrusions. In embodiments in which ribs are present, the ribs do not have any particular structure, but may be at least one of the following: continuous ribs, discontinuous ribs, longitudinally extending ribs, laterally extending ribs, diagonally extending ribs, integral ribs, non-integral ribs, mini-ribs, and combinations thereof. For example, the ribs may be discontinuous ribs and diagonally extending ribs. Protrusions are not ribs. An example of a protrusion may include, but is not limited to, a depression. When ribs, protrusions, or ribs and protrusions are formed on both sides of the substrate, the types of ribs, protrusions, or ribs and protrusions formed on each side or surface may be the same or different. For example, laterally extending ribs may be formed on one side or surface of the substrate, and longitudinally extending ribs may be formed on the other side or surface.

[0055] In some embodiments in which ribs, protrusions, or ribs and protrusions are formed on the surface of the substrate, one or more edge regions of the substrate may have no ribs, no protrusions, no ribs and protrusions, or one or more edge regions may only have mini-ribs, mini-protrusions, or mini-ribs and mini-protrusions. The mini-ribs or mini-protrusions may have a maximum height from the surface of the substrate to their highest point that is at most 100 microns to at most 250 microns from the surface of the substrate. In some embodiments, the maximum height may be at most 75 microns, at most 50 microns, at most 25 microns, at most 125 microns, at most 150 microns, at most 175 microns, at most 200 microns, or at most 225 microns. This type of structure may be useful when the final structure of the battery separator is a pouch or sleeve that includes welding of the edges of the substrate material to be formed. In such embodiments in which regions are formed that have no ribs or protrusions (or only have mini-ribs or mini-protrusions), it is preferable not to form a material layer in these regions either.

[0056] In some embodiments, the thickness of the substrate is 50 to 500 microns, 75 to 500 microns, 100 to 500 microns, 125 to 500 microns, 150 to 500 microns, 175 to 500 microns, 200 to 500 microns, 225 to 500 microns, 250 to 500 microns, 300 to 500 microns, 350 to 500 microns, 400 to 500 microns, 450 to 500 microns, 500 to 500 microns, 600 to 650 microns, 700 to 750 microns, 800 to 850 microns, 900 to 950 microns, 1000 to 1000 microns, 1100 to 1150 microns, 12 The thickness may range from 0 microns, 300-500 microns, 325-500 microns, 350-500 microns, 375-500 microns, 400-500 microns, 425-500 microns, 450-500 microns, or 475-500 microns. In embodiments in which ribs are formed on one or more surfaces of the substrate, the thickness of the substrate is the thickness of what is often referred to as the backweb, which is the substrate without regard to the height of the ribs formed thereon.

[0057] (2) Material layer A layer of material is formed on one or more partial or complete surfaces of the substrate described herein above.

[0058] The composition of the material layer is not particularly limited. In some embodiments, the layer may comprise, consist of, or consist essentially of a material having an oil absorption value of greater than 15g oil / 100g material, greater than 25g oil / 100g material, greater than 50g oil / 100g material, greater than 75g oil / 100g material, greater than 100g oil / 100g material, greater than 125g oil / 100g material, greater than 150g oil / 100g material, greater than 175g oil / 100g material, greater than 200g oil / 100g material, greater than 225g oil / 100g material, greater than 250g oil / 100g material, or greater than 275g oil / 100g material. The oil absorption value may be 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300 g of oil per 100 g of material. In some embodiments, the oil absorption value of a material is between 25 g of oil / 100 g of material and 300 g of oil / 100 g of material. Oil absorbency is used herein as a metric for the amount of battery acid that can be absorbed by a material. Oil absorbency may be measured by the appropriate ASTM test method for a particular material or any other appropriate method for measuring oil absorbency. The porosity, overall surface area, and other characteristics of a material are properties that may affect the oil absorption value of a given material.

[0059] In some embodiments, the substance has a density of 0.1 to 3.5 g / cm 3 Range: 0.2~3.5g / cm 3 Range: 0.3~3.5g / cm 3 Range: 0.4~3.5g / cm 3 Range: 0.5~3.5g / cm 3 Range: 0.6~3.5g / cm 3 Range: 0.7~3.5g / cm 3 Range: 0.8~3.5g / cm 3 Range: 0.9~3.5g / cm 3 Range: 1.0~3.5g / cm 3 Range: 1.1~3.5g / cm 3 Range: 1.2~3.5g / cm 3 range, 1.3~3.5g / cm 3range, 1.4~3.5g / cm 3 range, 1.5~3.5g / cm 3 range, 1.6~3.5g / cm 3 range, 1.7~3.5g / cm 3 range, 1.8~3.5g / cm 3 range, 1.9~3.5g / cm 3 Range: 2.0~3.5g / cm 3 range, 2.1~3.5g / cm 3 range, 2.2~3.5g / cm 3 range, 2.3~3.5g / cm 3 range, 2.4~3.5g / cm 3 range, 2.5~3.5g / cm 3 range, 2.6~3.5g / cm 3 range, 2.7~3.5g / cm 3 range, 2.8~3.5g / cm 3 range, 2.9~3.5g / cm 3 range, 3.0~3.5g / cm 3 range, 3.1~3.5g / cm 3 range, 3.2~3.5g / cm 3 range, 3.3~3.5g / cm 3 range, 3.4~3.5g / cm 3 In some embodiments, the bulk density is in the range of 0.1 g / cm 3 Less than or 3.5g / cm 3 It can be super.

[0060] In some embodiments, the material of the material layer may comprise, consist of, or consist essentially of silica, precipitated silica, fumed silica, talc, diatomaceous earth, polysulfone, polyester, PVC, and combinations thereof.

[0061] In some embodiments, the material may comprise, consist of, or consist essentially of one or more organic or inorganic particles having at least one of the following properties: hydrophilic, acidophilic, and acid-stable.

[0062] In some embodiments, the material may comprise, consist of, or consist essentially of a battery performance enhancing additive, such as, but not limited to, at least one selected from a wetting agent, a surfactant, a water loss reducing agent, a charge acceptance enhancer, a fatty alcohol, a zinc salt, carbon, and combinations thereof.

[0063] In some embodiments, the material has a single average particle size with a broad or narrow particle size distribution. In some embodiments, the material includes a first portion having a first average particle size and particle size distribution and a second, different (smaller or larger) average particle size and particle size distribution that may or may not overlap with the particle distribution of the first portion. Without wishing to be bound by any particular theory, it is believed that having at least two portions with different particle sizes and / or different particle size distributions may help increase the packing density of the material.

[0064] In some embodiments, the material layer may further comprise, consist of, or consist essentially of a binder. For example, in some embodiments, the material layer may comprise, consist of, or consist essentially of the above-mentioned materials and binders, or materials, binders, and additives, such as battery performance-enhancing additives. In some embodiments, the amount of binder in the material layer may be 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less.

[0065] The type of binder is not particularly limited. In some preferred embodiments, the binder may be a polymeric binder. In some embodiments, the binder may be insoluble, partially soluble, or soluble in battery acid, such as H2SO4. In some embodiments, it may be preferred that the binder be soluble or partially soluble in battery acid, such that when a battery separator described herein is placed in a lead-acid battery, a portion of the binder dissolves, rendering the material layer more porous than before the battery separator was placed in the battery.

[0066] In some embodiments, the material layer itself has a density of 0.1 to 3.5 g / cm 3 Range: 0.2~3.5g / cm 3 Range: 0.3~3.5g / cm 3 Range: 0.4~3.5g / cm 3 Range: 0.5~3.5g / cm 3 Range: 0.6~3.5g / cm 3 Range: 0.7~3.5g / cm 3 Range: 0.8~3.5g / cm 3 Range: 0.9~3.5g / cm 3 Range: 1.0~3.5g / cm 3 Range: 1.1~3.5g / cm 3 Range: 1.2~3.5g / cm 3 range, 1.3~3.5g / cm 3 range, 1.4~3.5g / cm 3 range, 1.5~3.5g / cm 3 range, 1.6~3.5g / cm 3 range, 1.7~3.5g / cm 3 range, 1.8~3.5g / cm 3 range, 1.9~3.5g / cm 3 Range: 2.0~3.5g / cm 3 range, 2.1~3.5g / cm 3 range, 2.2~3.5g / cm 3 range, 2.3~3.5g / cm 3 range, 2.4~3.5g / cm 3range, 2.5~3.5g / cm 3 range, 2.6~3.5g / cm 3 range, 2.7~3.5g / cm 3 range, 2.8~3.5g / cm 3 range, 2.9~3.5g / cm 3 range, 3.0~3.5g / cm 3 range, 3.1~3.5g / cm 3 range, 3.2~3.5g / cm 3 range, 3.3~3.5g / cm 3 range, 3.4~3.5g / cm 3 In some embodiments, the bulk density is in the range of 0.1 g / cm 3 Less than or 3.5g / cm 3 The bulk density may be measured before or after the layer of material (as part of a battery separator) is used in a lead-acid battery as described herein.

[0067] In some embodiments, a layer of material may be applied to the surface of a substrate described herein that includes ribs, protrusions, or ribs and protrusions. In some embodiments, a layer of material is applied to a surface or face of the substrate that has ribs or protrusions and a surface or face that has no ribs or protrusions.

[0068] A layer of material is applied to a surface or face having ribs, protrusions, or both ribs and protrusions, with the layer of material being applied in the areas between at least two ribs, at least two protrusions, or between the ribs and protrusions. In some embodiments, the layer of material may be present in the areas between all ribs, all protrusions, or all rib-to-protrusions. In some embodiments, the layer of material may be present only in the areas between some ribs, some protrusions, or some rib-to-protrusions. The layer of material may partially fill, completely fill, or overfill the areas between two ribs, two protrusions, or ribs and protrusions. Partially filled may mean that 1 to 99% of the area is filled. In some preferred embodiments, it may mean that 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more of the area is filled.

[0069] (3) Another optional layer In some embodiments, an optional layer may be provided in contact with the material layer. The composition of the optional layer is not particularly limited. In some embodiments, the layer may comprise, consist of, or consist essentially of one or more battery performance-enhancing additives described herein. In some embodiments, the layer may comprise, consist of, or consist essentially of one or more battery performance-enhancing additives described herein and one or more binders described herein. In some embodiments, the layer may comprise, consist of, or consist essentially of one or more battery performance-enhancing additives described herein, one or more binders described herein, and another additive.

[0070] The optional layer may have a thickness of 1 to 300 microns, 1 to 250 microns, 1 to 200 microns, 1 to 150 microns, 1 to 100 microns, or 1 to 50 microns.

[0071] In some embodiments, one or more battery performance enhancing additives may be present in the material layer and in another optional layer.

[0072] battery Any of the battery separators described herein may be used in lead-acid batteries, particularly flooded lead-acid batteries or sealed lead-acid (VRLA) batteries. In sealed lead-acid batteries, the battery separators described herein may replace at least one absorbent glass mat (AGM), some of the AGM, or all of the AGM. The battery separators described herein offer several advantages over AGM battery separators. For example, the battery separators are not infinitely compressible like AGM, which offers advantages in at least cylindrical battery cells. Infinite compressibility is also undesirable from a pressure resistance standpoint due to positive electrode active material (PAM) and negative electrode active material (NAM) expansion during battery operation.

[0073] The structure of a lead-acid battery is not particularly limited, but in a preferred embodiment, the lead-acid battery may include at least the following: (1) a positive electrode or plate, (2) a negative electrode or plate, (3) a battery separator described herein between the positive and negative plates, and (4) an electrolyte. The active layer of the battery separator described herein may be on the side in close contact with the positive plate, the side in close contact with the negative plate, or the side in close contact with both the negative and positive plates.

[0074] According to at least certain aspects, objects or embodiments, the present application or invention provides a method for implementing a PSoC. This application and the present invention may address, or at least partially address, some of the above-mentioned problems or issues known to be associated with typical lead-acid batteries operating at 1000 W. According to at least certain aspects, objects, or embodiments, the present application and the present invention, as described herein, provide a novel battery separator that preferably provides sufficient support for active material expansion, reduces, mitigates, or eliminates stratification, and will be highly oxidation-resistant. The same novel separator will preferably maintain the current advantages of existing separators, such as polyethylene separators, with low ionic resistance, excellent puncture resistance, envelope properties, and remain highly cost-effective. According to at least certain aspects, objects, or embodiments, the present invention preferably aims to satisfy at least these and other heretofore largely unmet needs.

[0075] At least one embodiment disclosed herein is a battery separator including a substrate, which may be polymeric and porous. The substrate may have ribs, protrusions, or ribs and protrusions on one or both surfaces or surfaces thereof. A material layer may be formed on at least one surface or surfaces of the substrate. The material layer may include a material having an oil absorption value of 15 g oil / 100 g material or greater. The battery separator disclosed herein is useful in lead-acid batteries, particularly flooded lead-acid batteries or sealed lead-acid (VRLA) batteries. The battery separators described herein have many advantages, including helping to reduce or prevent issues such as stratification and other issues that can reduce battery performance or battery life.

[0076] In some embodiments, the lead acid battery may be a cylindrical or prismatic cell lead acid battery, an accumulator, a storage battery, or the like.

[0077] The separator may be rolled, for example, to set a final height or thickness, to compress coatings or materials, and / or the like.

[0078] In the batteries described herein, the battery separator does one, two, three, or all four of the following: immobilizes at least a portion of the acid-containing electrolyte, which promotes stratification; is not infinitely compressible, which aids in cell fabrication; and constrains the active material (NAM or PAM) in at least one of the positive or negative plates, since an unconstrained NAM or PAM may fall off; and improves oxidation resistance, which allows for the use of thinner, more porous base materials in the separators described in the Examples below.

[0079] As used herein, solubility in an acid may, in some cases, be determined by looking at the oxidation resistance of a material (e.g., a binder) in that acid. Low oxidation resistance may indicate a soluble binder, while high oxidation resistance may indicate an insoluble binder. Partially soluble binders will have a moderate range of oxidation resistance (high to low).

[0080] As used herein, the hydrophilicity of a material may, in some cases, be determined by looking at the wet-out time of a separator having a layer of material comprising, consisting of, or consisting essentially of that material. For example, a wet-out time of less than 10 minutes, less than 9 minutes, less than 8 minutes, less than 7 minutes, less than 6 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, or less than 30 seconds. In some cases, less than 3 minutes is preferred.

[0081] As used herein, the acidophilicity of a material may be determined, in some cases, by looking at the wet-out time of a separator having a layer of material comprising, consisting of, or consisting essentially of the material. For example, the wet-out time may be less than 10 minutes, less than 9 minutes, less than 8 minutes, less than 7 minutes, less than 6 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, or less than 3 minutes. In some cases, less than 3 minutes is preferable.

[0082] As used herein, the term acid stability may, in some cases, be determined by looking at the oxidation resistance of a material in the acid. A material with low oxidation resistance is considered to be less stable in acid than a material with high oxidation resistance. A weight loss test may be performed to measure oxidation resistance. [Example]

[0083] Example 1 - PE ribbed substrate + silica material layer on ribbed side for use in flooded lead acid batteries As a starting point, the novel invention will first be described with reference to a separator used in an enhanced flooded battery (EFB). An EFB has a typical electrode spacing of approximately 0.8 mm. A PE separator (substrate) is placed in this spacing. The separator's backweb is typically 0.20 mm, with ribs protruding from this surface an additional 0.60 mm, resulting in a total separator thickness of 0.80 mm. A typical automotive separator may have 11 to 30 ribs across its surface. In some embodiments, the invention takes a typical PE separator and applies highly porous silica particles with an oil absorption value of greater than 15 g oil / 100 g silica to the spaces between the ribs. To function in highly automated equipment, the silica will need to be bonded to the separator substrate and adjacent silica particles. Bonding or adhesion to the silica can be achieved by appropriate selection of currently available chemicals, for example, using binders described herein.

[0084] To begin with, silica agglomerates are approximately 85% porous by themselves. Then, when the particles are randomly arranged in the spaces between the ribs, they create a semi-rigid porous structure that serves a number of purposes. First, the semi-rigid porous structure will uniformly support the active material, which expands during discharge. In this way, the active material is unsupported and will expand to form large crystals of stable lead sulfate, effectively non-porous, preventing acid from reacting with the active material. These large areas are dominated by lead sulfate, which is an effective insulator and a highly effective barrier against acid intimate contact with the active lead particles. If left in this state long enough, the large areas of lead sulfate will lose contact with the other active material, causing electrode surface area to shed. The advantage of this invention is that the silica-coated separator will uniformly support the active material, prevent areas of expansion, and create optimal utilization of the active material, extending life when active material shedding is the cause. Applications that use laminates such as glass mats or paste paper to minimize active material shedding can suppress these and utilize this invention.

[0085] After shedding, the highly porous silica layer with its high surface area would be useful for immobilizing the acid, preventing stratification. During charging, pure sulfuric acid is produced at the electrode surface. This acid is denser than bulk acid and would tend to stratify. When the silica layer is pressed against the positive electrode, the interstitial porous structure of the silica would hold the acid in place. The primary method for overcoming stratification is to overcharge the battery to produce oxygen and hydrogen through the electrolysis of water. These gases would form in the acid and vent through the vent port. When they do, the gases would carry the heavier liquid upward and mix with the acid. However, when operating at a partial charge, the battery may not necessarily know it is overcharged, and therefore there is no primary means of acid mixing. Additionally, if we can prevent stratification, we no longer need to overcharge. Minimizing the number of overcharges would reduce water loss and slow the rate of grid corrosion.

[0086] Another advantage of the present invention can be seen with respect to oxidation corrosion. When electrodes are thinned, the associated separator spacing is also thinned. Therefore, the opportunity for oxidation corrosion in the separator increases. With respect to this corrosion, it is important to keep the backweb thickness or the continuous substrate of the separator intact. This is important. If compromised with a hole, crack, or tear, this is where electronic conductance will occur from the counter electrode, resulting in a short circuit. When oxidative corrosion is initiated at the positive electrode, the silica-coated surface will provide an additional layer of oxidation protection. With this silica layer on the substrate, one could even consider the possibility of making substrates thinner (<150 microns) or with greater porosity (>62%), or a combination of both. A separator with a thinner backweb and higher porosity would result in lower separator ionic or electrical resistance and therefore provide more power for the battery during heavy discharge.

[0087] All of the described advantages can also be applied to lead-acid batteries used in other applications, such as golf carts, renewable energy, backup power, and energy solutions for electric fork trucks. In these applications, the electrode spacing is typically larger, and therefore the overall thickness of the separator is also larger than that found in automotive batteries. Furthermore, the application of the advantages of this new separator can also be applied in the same way.

[0088] Example 2 - PE ribbed substrate + silica material layer on ribbed side used in sealed lead acid batteries (VRLA) Example 1 describes a flooded lead-acid battery. However, the silica-coated separator (PE ribbed substrate on the ribbed side + silica material layer) described above can also function in non-flooded applications, so-called starve electrolytes in sealed lead-acid batteries (VRLA). These have only a few configurations. First, the configuration is commonly referred to as a gel or dry-fit battery. In this application, a polyethylene or cross-linked separator and acid electrolyte are mixed with fumed silica to create a thixotropic state and added to the battery. In this state, the electrolyte is immobilized and prevents stratification. With this particular invention, a thixotropic state is not necessary; acid can be added to the battery and the silica-coated separator will serve to immobilize the electrolyte.

[0089] Another type of VRLA battery is often called an AGM battery. Here, the separator is made of absorbent microfiber glass mat, also known as an AGM separator. While these separators immobilize acid well, they have several deficiencies. Generally, the pores of AGM separators range from 5 to 25 microns and therefore do not provide sufficient protection against short circuits. Therefore, when AGM batteries are used in deep-cycle applications, they may fail due to short circuits. Therefore, the idea is to use a submicron substrate, such as a PE separator, and coat it with highly porous silica. The PE separator or substrate would provide short circuit protection while immobilizing the acid using a silica layer. This invention can be very useful in AGM batteries with very thin plate spacing (e.g., <1.0 mm), such as e-bikes, e-cars, thin foil, or bipolar batteries. The battery separator described herein can replace any one of the AGMs in an AGM VRLA battery.

[0090] Example 3 There is another embodiment of the present invention that is worth considering. The current immediate application is to coat silica onto an existing separator, and thus far the examples have described a PE separator. However, silica can be coated onto other types of separators, such as those made from rubber, cross-linked phenolic resin, and synthetic wood pulp. If the silica layer provides a pore structure small enough to prevent the formation of pores (<5 microns), then submicron materials are no longer necessary. Therefore, another embodiment is to coat a thin nonwoven web with the silica layer. In this method, the nonwoven layer acts as a carrier web that allows the silica layer to be transferred to the battery. This nonwoven can be polymeric or any of the materials currently used to manufacture paste paper. It can even be made from cellulose materials such as those used in

[0091] Example 4 In this example, the PE substrate of Example 1 is coated with a mixture of silica and carbon on the negative side of the substrate, or the side that faces the negative electrode or plate in a battery.

[0092] Example 5 In this example, the PE substrate of Example 1 has silica coated over the entire surface of the substrate. In this method, a separator can be used to encase the electrode or electrode plate.

[0093] Example 6 In this example, the PE substrate of Example 1 is coated with silica over most of its surface, with the exception of the outer strip, which preferably has no ribs or only mini-ribs, allowing the separator to be enveloped and enclosed within itself.

[0094] Example 7 In this embodiment, the PE substrate is microporous but does not have ribs or protrusions. A layer of silica material is applied to at least one surface thereof. This may be a partial or full surface coating. In Example 7a, silica is applied to both surfaces or surfaces of the PE substrate. Silica may be applied to the full or partial surface.

[0095] Example 8 This example is similar to Example 1 except that the silica layer has a moisture loss additive mixed with the silica.

[0096] Example 9 This example is similar to Example 1 except that the PE substrate is replaced by a nonwoven material or woven fabric.

[0097] Example 10 This example is similar to Example 1, except that the carbon may be applied to the negative electrode surface or to the surface of the substrate.

Claims

1. a polymeric substrate (flexible spine, preferably porous or microporous, but may be non-porous); and a layer of material comprising, consisting of, or consisting essentially of a material having an oil absorbency of greater than 15 g oil / 100 g material, the layer of material being provided on at least one surface of said polymeric substrate; Including, battery separator.

2. 10. The battery separator of claim 1, wherein the material has an oil absorbency of greater than 25g oil / 100g material, between 25g oil / 100g material and 100g oil / 100g material, between 25g oil / 100g material and 200g oil / 100g material, or between 25g oil / 100g material and 300g oil / 100g material.

3. 3. The battery separator of claim 2, wherein the material layer is disposed on two or more sides of the polymer substrate.

4. The polymer substrate is a porous polymer membrane having a positive electrode surface and a negative electrode surface, and each of the positive electrode surface and the negative electrode surface optionally has ribs, protrusions, or both ribs and protrusions; and forming the material layer on at least one of the positive electrode surface, the negative electrode surface, or both the positive electrode surface and the negative electrode surface; 10. The battery separator of claim 1.

5. 5. The battery separator of claim 4, wherein the material layer is formed on the positive electrode side of the polymeric porous membrane.

6. 5. The battery separator of claim 4, wherein the material layer is formed on the negative electrode side of the polymeric porous membrane.

7. 5. The battery separator according to claim 4, wherein the material layers are formed on the positive electrode surface and the negative electrode surface of the polymeric porous membrane.

8. 5. The battery separator of claim 4, wherein the positive electrode surface comprises ribs, protrusions, or both ribs and protrusions.

9. 5. The battery separator of claim 4, wherein the negative electrode surface comprises ribs, protrusions, or both.

10. 5. The battery separator of claim 4, wherein both the positive electrode surface and the negative electrode surface include ribs, protrusions, or both.

11. 11. The battery separator of claim 8, wherein the positive electrode surface or the negative electrode surface comprises ribs, the ribs being at least one selected from continuous ribs, discontinuous ribs, longitudinally extending ribs, laterally extending ribs, diagonally extending ribs, integral ribs, non-integral ribs, and mini-ribs.

12. 12. At least one outer edge of the polymeric porous membrane has no ribs or protrusions or only mini-ribs or mini-protrusions, the mini-ribs or mini-protrusions having a height of at most 100 microns to 250 microns from the surface of the polymeric porous membrane.

10. The battery separator according to any one of claims 1 to 9.

13. 13. The battery separator according to any one of claims 8 to 12, wherein the material layer is provided between at least two ribs, between at least two protrusions, or between a rib and a protrusion, but not between any two mini-ribs or mini-protrusions.

14. 14. The battery separator of claim 13, wherein the material layer completely fills, partially fills, or overfills the area between at least two ribs, between at least two protrusions, or between a rib and a protrusion.

15. 15. The battery separator of claim 14, wherein the material layer completely fills the area between at least two ribs, between at least two protrusions, or between a rib and a protrusion.

16. 15. The battery separator of claim 14, wherein the material layer partially fills the area between at least two ribs, between at least two protrusions, or between a rib and a protrusion.

17. 15. The battery separator of claim 14, wherein the material layer overfills the area between at least two ribs, between at least two protrusions, or between a rib and a protrusion.

18. 3. The battery separator of claim 1 or claim 2, wherein the polymer substrate is a polymeric porous membrane and the average pore size is less than about 1 micron.

19. 3. The battery separator of claim 1 or claim 2, wherein the polymeric porous substrate is microporous, nanoporous, macroporous, or mesoporous.

20. 20. The battery separator of claim 18, wherein the polymeric porous membrane comprises a polyolefin.

21. 21. The battery separator of claim 20, wherein the polyolefin is at least one of polyethylene, polypropylene, and blends or copolymers thereof.

22. 21. The battery separator of claim 20, wherein the polymeric porous membrane further comprises a filler.

23. The polymeric porous membrane has ribs, protrusions, or both ribs and protrusions on at least one surface thereof, and the material layer is made of one of the following: a surface of the polymeric porous membrane that includes ribs, protrusions, or both ribs and protrusions; or A surface of the porous polymer membrane that does not have ribs, protrusions, or both ribs and protrusions.

5. The battery separator of claim 4, wherein the separator is provided on at least one surface of the battery.

24. 24. The battery separator of claim 23, wherein the material layer is disposed on a side of the polymeric porous membrane that includes ribs, protrusions, or both ribs and protrusions.

25. 24. The battery separator of claim 23, wherein the material layer is disposed on a side of the polymeric porous membrane that does not have ribs, protrusions, or both ribs and protrusions.

26. The material layer may be: a surface of the polymeric porous membrane that includes ribs, protrusions, or both ribs and protrusions; and A surface of the porous polymer membrane that does not have ribs, protrusions, or both ribs and protrusions.

24. The battery separator of claim 23, wherein the first and second electrodes are disposed on both sides of the separator.

27. The material layer or the material of the material layer has a density of 0.1 to 3.5 g / cm ３ 3. The battery separator of claim 1 or claim 2, having a bulk density of

28. 3. The battery separator of claim 1 or 2, wherein the material layer further comprises, consists of, or consists essentially of a binder.

29. 30. The battery separator of claim 28, wherein said binder is present in an amount less than 50%.

30. 30. The battery separator of claim 29, wherein said binder is present in an amount of 1 to 20%.

31. The binder is H ２ SO ４ 31. The battery separator of any one of claims 28 to 30, which is soluble, partially soluble, or insoluble in battery acids such as

32. The binder is H ２ SO ４ 32. The battery separator of claim 31, wherein the battery separator is soluble in battery acids such as

33. The binder is H ２ SO ４ 32. The battery separator of claim 31, wherein the battery separator is partially soluble in battery acids such as

34. The binder is H ２ SO ４ 32. The battery separator of claim 31, wherein the battery separator is insoluble in battery acids such as

35. 30. The battery separator of claim 1, claim 2, or claim 28, wherein the material layer further comprises, consists of, or consists essentially of at least one other material.

36. 30. The battery separator of claim 1, claim 2, or claim 28, wherein the material is at least one selected from the group consisting of silica, precipitated silica, fumed silica, talc, diatomaceous earth, polysulfone, polyester, PVC, and combinations thereof.

37. 30. The battery separator of claim 1, claim 2, or claim 28, wherein the material is an organic or inorganic particle that is at least one of hydrophilic, acidophilic, and acid-stable.

38. 30. The battery separator of claim 1, claim 2, or claim 28, wherein the material comprises particles of different sizes.

39. 36. The battery separator of claim 35, wherein the at least one other substance is selected from the group consisting of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, any other battery performance enhancing additive, and combinations thereof.

40. 3. The battery separator according to claim 1 or 2, wherein the another material layer is provided on top of the material layer.

41. 5. The battery separator of claim 4, wherein at least one of the positive and negative electrode surfaces does not include any ribs or protrusions.

42. 42. The battery separator of claim 41, wherein both said positive and negative electrode surfaces are free of any ribs or protrusions.

43. 3. The battery separator of claim 1 or claim 2, wherein the polymer-based material has an oil content of 1-20%.

44. 44. The battery separator of claim 43, wherein the oil content of the polymeric base material is 1-10%.

45. 45. The battery separator of claim 44, wherein the oil content of the polymeric base material is 1-5%.

46. 3. The battery separator of claim 1 or 2, wherein the polymeric substrate is a nonwoven or woven polymeric substrate.

47. 3. The battery separator according to claim 1 or 2, wherein the polymer substrate is a sheet or an envelope.

48. 1. A lead-acid battery, including a flooded lead-acid battery or a sealed lead-acid battery, comprising: a negative electrode plate; a positive electrode plate; an acid-containing electrolyte; a battery separator between a positive plate and a negative plate, the battery separator being the battery separator of any one of claims 1 to 47 or claims 69 to 72; and Lead acid batteries including.

49. 49. The lead-acid battery of claim 48, wherein the lead-acid battery is a cylindrical cell lead-acid battery.

50. 49. The lead-acid battery of claim 48, wherein the lead-acid battery is a prismatic cell lead-acid battery.

51. 49. The lead acid battery of claim 48, wherein the material layer is formed between the polymer substrate and the positive electrode plate.

52. 49. The lead acid battery of claim 48, wherein the material layer is formed between the polymer substrate and the negative electrode plate.

53. 49. The lead-acid battery of claim 48, wherein the material layer is formed both between the polymer substrate and the positive electrode plate and between the polymer substrate and the negative electrode plate.

54. 49. The lead-acid battery of claim 48, wherein the lead-acid battery is a sealed lead-acid battery.

55. 49. The lead-acid battery of claim 48, wherein the lead-acid battery is a flooded lead-acid battery.

56. 49. The lead-acid battery of claim 48, wherein at least one additional layer is formed between the polymer substrate and the positive plate, between the polymer substrate and the negative plate, or both between the polymer substrate and the positive plate and between the polymer substrate and the negative plate.

57. 57. The lead acid battery of claim 56, wherein the additional layer comprises at least one of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, any other battery performance enhancing additive, and combinations thereof.

58. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 49. The lead acid battery of claim 48, wherein the battery performs or exhibits at least one of the following:

59. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 59. The lead acid battery of claim 58, which performs or exhibits at least two of the following:

60. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 59. The lead acid battery of claim 58, wherein the battery performs or exhibits at least three or all four of the following:

61. 73. A sealed lead acid battery (VRLA battery), wherein the improvement comprises replacing at least one absorbent glass mat with a battery separator according to any one of claims 1 to 47 or claims 69 to 72.

62. 62. The VRLA battery of claim 61, wherein the battery is a cylindrical cell battery.

63. 62. The VRLA battery of claim 61, wherein the battery is a prismatic cell battery.

64. 62. The VRLA battery of claim 61, wherein at least one additional layer is formed between the polymeric substrate and a positive plate, between the polymeric substrate and a negative plate, or both between the polymeric substrate and a positive plate and between the polymeric substrate and a negative plate.

65. 65. The VRLA battery of claim 64, wherein the additional layer comprises at least one of carbon, a water loss reducing agent, a fatty alcohol, a surfactant, a wetting agent, a zinc salt, any other battery performance enhancing additive, and combinations thereof.

66. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 62. The VRLA battery of claim 61, exhibiting or performing at least one of:

67. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 67. The VRLA battery of claim 66, wherein the VRLA battery performs or exhibits at least two of the following:

68. The battery separator comprises: immobilizing at least a portion of the acid-containing electrolyte; Improved oxidation resistance; It is not infinitely compressible and: constraining an active material (NAM or PAM) in at least one of the positive or negative plates; 67. The VRLA battery of claim 66, wherein the VRLA battery performs or exhibits at least three or all four of the following:

69. 10. The battery separator of claim 1 or claim 4, wherein the polymeric substrate has a thickness of 50 to 500 microns.

70. 70. The battery separator of claim 69, wherein the combined thickness of said polymeric substrate and said material layer is between 100 microns and 4 mm.

71. 70. The battery separator of claim 69, wherein said polymeric substrate has a thickness of less than 150 microns.

72. 5. The battery separator of claim 1 or claim 4, wherein the polymeric substrate has a porosity of greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, or greater than 90%.

73. As shown, described, or claimed herein, the objects or embodiments of the present application or invention may address or at least partially address some of the above-mentioned known problems or issues associated with typical lead acid batteries operating in PSoC, may provide a new battery separator that preferably provides sufficient support for active material expansion, reduces, mitigates, or eliminates stratification, and may be highly oxidation resistant, and may also preferably maintain the current advantages of existing separators such as polyethylene separators, including low ionic resistance, excellent puncture resistance, envelope properties, while remaining highly cost-effective, and may provide or address at least these and other heretofore largely unmet needs, and / or the like.

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