Battery separators, battery gelation composite substrates, battery separator coated membranes, related methods, and cells, batteries or systems incorporating the same

Abstract

A coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane is provided comprising a microporous substrate; and a coating on one or both sides of the microporous substrate. The coating comprises a polymeric binder and inorganic filler or siliceous material. In some examples, the separator is coated on one or both sides of the microporous substrate or membrane, wherein the coating comprises a polymeric binder, siliceous material, and carboxymethyl cellulose (CMC). In some examples, the microporous substrate may be a ribbed microporous substrate comprising polyethylene. Also provided are batteries including the coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane. Such batteries may be improved flooded lead acid batteries, VRLA gel batteries, AGM batteries, storage batteries, or flow batteries.

Description

BATTERY SEPARATORS, BATTERY GELATION COMPOSITE SUBSTRATES, BATTERY SEPARATOR COATED MEMBRANES, RELATED METHODS, AND CELLS, BATTERIES OR SYSTEMS INCORPORATING THE SAMETECHNICAL FIELD

[0001] The present disclosure relates to coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and cells, batteries or systems incorporating the same.BACKGROUND

[0002] Lead acid batteries operating at a partial state of charge are those operating at a state of charge between about 65% to about 90% or less. At partial charge, gas bubbles are not generated, and the internal mixing of the electrolyte is substantially reduced, leading to acid stratification within the battery. Acid stratification in lead acid batteries often leads to faster sulfation, reduced capacity, damage to the battery plates or electrodes, and eventual battery failure.

[0003] Stratification of battery electrolyte has challenged the flooded lead acid battery (FLA) since its inception, especially in cycling applications where the electrolyte density gradient stratification exacerbates battery sulfation. Standard flooded lead acid battery separators do not regulate the distribution of the acid and the resultant acid stratification causes instability for monitoring systems measuring an open circuit voltage (OCV) that represents the charge state of the FLA battery. While absorbent glass mat (AGM) separator technology may provide at least a partial solution to these stratification issues, improving the efficiency of battery management systems, AGM technology has increased complexity and cost.

[0004] In some instances, acid stratification can be avoided using valve regulated lead acid (VRLA) technology where the acid is immobilized by either a gelled electrolyte (VRLA-Gel or Gel battery) and / or by an absorbent glass mat (AGM) battery separator system (VRLA-AGM or AGM battery). In contrast to the freely-fluid electrolyte in flooded lead acid batteries (FLA), in VRLA batteries (VRLA are also known as sealed or maintenance free batteries) the electrolyte is absorbed on a fiber or fibrous material, such as a glass fiber mat, a polymeric fiber mat, a gelled electrolyte, and so forth. However, VRLA battery systems are substantially more expensive to manufacture than flooded battery systems. VRLA-AGM technology in some instances, may be more sensitive to overcharging, may dry out in high heat, may experience a gradual decline in capacity, and may have a lower specific energy. Similarly, in some instances, VRLA-Gel technology may have higher internal resistance and may have reduced charge acceptance.

[0005] There is a growing need for 12V lead acid auxiliary batteries, which are a critical on-board component for electric vehicles (EVs), and in the range of lower emission vehicles such as hybrid vehicles. The 12V lead auxiliary battery provides back up power for safety relevant features such as power steering and brake boosting. Not to mention, these auxiliary batteries are used to power electronic accessories in EVs and non-EVs, including comfort features such as radio, sound systems, security systems, cameras, and navigation systems.

[0006] Due to the harsh demands placed on these auxiliary batteries, they are operating at a partial state of charge, which as explained previously, makes them prone to acid stratification. In some cases, acid stratification in these auxiliary batteries may even be worse than in other types of lead acid batteries also operating at a partial state of charge.

[0007] Thus a need exists for novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse orientedcoated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and cells, batteries or systems incorporating the same.SUMMARY

[0008] The following presents a simplified summary of one or more examples of the present disclosure, in order to provide a basic understanding of such examples. This summary is not an extensive overview of all contemplated examples and is intended to neither identify key or critical elements of all examples nor delineate the scope of any or all examples. Its sole purpose is to present some concepts of one or more examples of the present disclosure in a simplified form as a prelude to the more detailed description that is presented later herein.

[0009] In accordance with at least certain embodiments, aspects or objects of the present invention or disclosure, there are disclosed or provided novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and / or batteries incorporating the same.

[0010] In accordance with at least certain embodiments, aspects or objects of the present invention or disclosure, there are disclosed or provided novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and cells, batteries or systems incorporating the same that may address the prior issues or needs with sulfation, reduced capacity, damage to the battery plates or electrodes, and eventual battery failure especially in Partial State of Charge (PSoC) batteries, acid stratification, acid stratification in FLA batteries, acid stratification in auxiliary batteries, acid stratification in FLA auxiliary batteries, reduced cycle life, reduced cycle life in FLA batteries, reduced cycle life inauxiliary batteries, reduced cycle life in auxiliary FLA batteries, sulfation, sulfation in FLA batteries, sulfation in auxiliary batteries, sulfation in auxiliary FLA batteries, reduced capacity, reduced capacity in FLA batteries, reduced capacity in auxiliary batteries, reduced capacity in auxiliary FLA batteries, acid starvation at the negative plate, positive active material (PAM) shedding at the positive plate, and / or combinations or subcombinations thereof.

[0011] In one example, a battery separator is provided, the separator comprising a microporous substrate having a first side and an opposing second side, and a coating adjacent at least one of the first side and the opposing second side, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0012] In a preferred example a separator is provided oriented such that a major rib faces the negative active material (NAM) of a negative plate or electrode and a flat, planar, minor rib, mini-rib, or cross-rib may face the positive active material (PAM) of a positive plate or electrode. This This separator orientation is referred to herein as a reverse orientation as it is contrary to typical, historical or normal separator orientation in a lead acid battery where a major rib is provided next to the PAM and a flat, planar, minor rib, mini-rib, or cross-rib is provided next to a NAM. The possibly preferred reverse orientation of the present disclosure or invention provides a large electrolyte and oxygen reservoir next to the NAM for sufficient recombination of H2O. The possibly preferred homogenous, consistent, uniform gelation layer formed form from a coating comprising a mixture of a polymeric binder and a siliceous material a or a silicious filler coated on a flat, minor rib, mini-rib, or cross-rib separator oriented to be in an intimate contact to the PAM by as much as 100% contact may address, reduce, eliminate or retard H2SO4 stratification.

[0013] In one preferred example, a battery separator is provided such that a separator comprising a microporous substrate having a first side with high surface contact “area” adjacent to the PAM and- or a second side with high surface contact “area” adjacent to the NAM on an opposing side. A coating adjacent at least one of the first side with high surface “area” and the opposing second side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0014] In one possibly most preferred example, a battery separator is provided suchthat a separator comprising a microporous substrate having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a flooded lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0015] In another possibly most preferred example, a battery separator is provided in a reverse orientation with the typical negative side ribs adjacent the PAM and the typical positive side ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0016] In yet another possibly most preferred example, a lead acid battery separator is provided in a reverse orientation with the typical negative side minor ribs adjacent the PAM and the typical positive side major ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0017] In still yet another possibly most preferred example, a lead acid battery separator for a FLA, VRLA, VRLA-Gel, or VRLA-AGM cell, battery or system is provided in a reverse orientation with the typical negative side minor ribs adjacent the PAM and the typical positive side major ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0018] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side,coated or treated silica filled polyethylene membranes with ribs on both sides, or reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides surprisingly and unexpectedly may significantly extend the Partial State of Charge (PSoC) cycle life of FLA batteries by an impressive 500%.

[0019] Lead-acid batteries maintain a decisive cost advantage over lithium-ion, driven by a well-established U.S. manufacturing base, a robust recycling infrastructure, and a complete reliance on domestic materials and parts. This strategic position makes lead-acid a formidable player in the U.S. battery electric vehicle (BEV) market, where its role as an auxiliary battery technology remains crucial. While lead-acid batteries typically last 5-8 years under normal conditions, far shorter than the purported 10-15-year lifespan of most BEV lithium-ion propulsion batteries, they must evolve to stay relevant. To remain competitive, lead-acid technology must enhance its performance and longevity, while continuing to leverage its unparalleled cost and domestic supply advantages.

[0020] Lead-acid batteries are particularly prone to acid stratification, especially during Partial State of Charge (PSoC) activities, which is typical of start-stop operation. Acid stratification occurs primarily during the charging cycle, when concentrated acid is released as a byproduct of the lead-acid reaction, mainly from the positive plate. This typically can be mitigated by fully charging, and overcharging the battery generating hydrogen / oxygen gas bubbles to rise and mix the electrolyte. However, these gas bubbles may be combustible , the gassing may cause acid to spew out of the container, and overcharging is seen as squandering useful energy. Should acid stratification be left unchecked, several other challenges will arise, including miscommunication with the Battery Management System (BMS), which monitors the battery's State of Health (SoH), as well as accelerated sulfation, ultimately reducing the battery’s cycle life.

[0021] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, or reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides surprisingly and unexpectedly may be used in a reverse separator orientation for improving Partial State of Charge (PSoC) lead-acid battery performance. Briefly, the separatoris traditionally oriented with the major ribs facing the positive plate (minor rib faces negative plate), allowing more acid to the otherwise acid-deficient positive plate. However, PSoC operation and this typical orientation may instead create an acid deficiency at the negative plate during its operation. By applying the inventive reverse separator orientation and placing the gelation coating or layer to the minor rib side against the PAM NAM of the positive plate, the system becomes more effective. In this new configuration, the coating or layer in the presence of concentrated acid, will form a gelation network that encapsulates and holds the acid in place for subsequent reactions. The gelling, combined with slight compression (such as only 5% well- known in the arts to be slight compression), pushes the separator up against the positive plate, preventing Positive Active Material (PAM) shedding and reducing the precipitation of concentrated acid. Additionally, having the major ribs facing the negative plate allows more acid to reach the negative plate, overcoming the previous acid deficiency. The free-flowing acid towards the negative plate, mitigates power loss often associated with fully gelled systems like Gel batteries. As a result, these synergistic effects surprisingly, unexpectedly, and favorably yielded a remarkable improvement in PSoC performance, achieving a 5 times enhancement in two standardized lifecycle tests — 17.5% PSoC and 50% Depth of Discharge (DoD) tests.

[0022] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, or coated or treated silica filled polyethylene membranes, surprisingly and unexpectedly may improve Flooded Lead Acid Batteries (FLB) to perform more like and compete with AGM batteries and may even improve Valve-Regulated Lead Acid Batteries (VRLA), VRLA-Gel Batteries and VRLA-AGM Batteries.

[0023] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, a novel composite layer or coating is applied to a silica filled base PE separator or membrane. When combined with a reverse separator orientation, this inventive approach may yield a remarkable 500% enhancement in Partial State of Charge (PSoC) cycle life performance. Specifically, by applying the gelation layer to the minor rib and inverting the orientation, the gelation layer faces the positive plate, forming a gelation network in the presence of acid. This network effectively immobilizes the generated, concentrated acid, facilitating subsequent reactions. Concurrently, slight compression (such as only 5%) pushes the separator against the positive plate, mitigating the shedding of Positive Active Material (PAM). The reverse orientation major ribs, now positioned against the negative plate, ensureadequate acid supply, overcoming acid deficiency. This synergistic approach has demonstrated a remarkable 5x improvement in PSoC performance across two standardized life-cycle tests: 17.5% PSoC and 50% Depth of Discharge (DoD) tests.

[0024] Recognizing the promising results of this new technology, Daramic, LLC of Charlotte, NC has been selected as a collaborator for a US Department of Energy (DOE) project focused on developing improved 12V Lead Acid Batteries for Safety Critical Electric Vehicle Applications aimed to address the critical need for enhanced 12V auxiliary battery performance in the growing electric vehicle market.

[0025] Since the advent of Battery Electric Vehicles (BEVs), a 12V auxiliary (AUX) battery has been an indispensable component of the vehicle's electrical system. While lithium-ion batteries are occasionally employed, lead acid batteries remain the most cost-effective solution for this critical function. The U.S. lead acid battery industry boasts a mature and robust manufacturing base, with a recycling rate exceeding 99% and minimal reliance on foreign materials. These factors solidify the position of lead acid batteries as the preferred AUX battery technology for the burgeoning U.S. BEV market.

[0026] A significant challenge in extending the service life of enhanced flooded lead acid batteries (EFB) auxiliary batteries is the detrimental effects of cycling, primarily sulfation of the negative plate due to acid stratification and the shedding / wear and tear of the positive plate. Acid stratification elevates the open-circuit voltage, misleading the Battery Management System (BMS) into undercharging the battery, ultimately leading to premature failure. As previously discussed, Daramic's innovative new gelation layer or coating separator technology, featuring a microporous polyethylene separator with a gelation composite layer, effectively addresses this issue. By absorbing and immobilizing the electrolyte, the gelation layer (preferably against the PAM, with major ribs against the NAM) significantly mitigates acid stratification and consequently enhances PSoC cycle life.

[0027] In at least one aspect, object or embodiment, the microporous substrate, separator, or separator membrane is shaped to receive an electrode of a battery such as a lead acid battery or FLA. For example, the microporous substrate, separator, or separator membrane may be a wrap, a V or U, a sleeve, a gauntlet, an envelope or pocket, a hybrid envelope or pocket with slits or openings (in the base, seams, and / or sides), a positive electrode envelope (“positive enveloping separator” or “P-wrapped”), a negative electrode envelope (“negative enveloping separator” or “N-wrapped”), may be a folded or have a sealed crease edge, the lateral edges may be continuously orintermittently sealed seam edges, the edges may be bonded or sealed by adhesive, heat, ultrasonic welding, and / or the like, or any combination thereof.

[0028] In at least one possibly preferred aspect, object or embodiment, the microporous substrate, separator, or separator membrane is a reverse oriented microporous substrate, separator, or separator membrane shaped to receive an electrode of a battery such as a lead acid battery or FLA. For example, the reverse orientated microporous substrate, separator, or separator membrane may be a wrap, a V or U, a sleeve, a gauntlet, an envelope or pocket, a hybrid envelope or pocket with slits or openings (in the base, seams, and / or sides), a positive electrode envelope (“positive enveloping separator” or “P-wrapped”), a negative electrode envelope (“negative enveloping separator” or “N-wrapped”), may be a folded or have a sealed crease edge, the lateral edges may be continuously or intermittently sealed seam edges, the edges may be bonded or sealed by adhesive, heat, ultrasonic welding, and / or the like, or any combination thereof.

[0029] In one aspect, alone or in combination with any previous aspect, the microporous substrate is configured as a sheet or rolled sheet of between 25 to 4000 microns thickness such as between 25 to 1500 microns thickness. In one aspect, alone or in combination with any previous aspect, the microporous substrate is a polyolefin membrane, a filled polyolefin porous membrane, a glass mat, an absorptive glass mat (AGM), a woven, a non-woven, a PVC membrane, a phenolic membrane, a cellulosic material or membrane, or combinations thereof.

[0030] In one aspect, alone or in combination with any previous aspect, the microporous substrate is filled with at least filler of silica, synthetic wood pulp (“SWP”), lignins, glass fibers, synthetic fibers, cellulosic fibers, fishbone meal, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, clay, aluminum silicate, sodium aluminum silicate, aluminum polysilicate, alumina silica gels, glass particles, carbon black, activated carbon, carbon fibers, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, lead oxide, tungsten, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate, magnesium carbonate, 5-20 weight percent aromatic oil, pigment, additives, and combinationsthereof. In one aspect, alone or in combination with any previous aspect, the filled polyolefin porous membrane comprises a weight ratio of the at least one filler to polyolefin from 2.5:1.0 to 5.0:1.0 or from 1.5:1.0 to 8.0:1.0.

[0031] In one aspect, alone or in combination with any previous aspect, the coating is positioned on the at least one of the first side and the opposing second side. In one aspect, alone or in combination with any previous aspect, the coating is directly adjacent the at least one of the first side and the opposing second side. In one aspect, alone or in combination with any previous aspect, the coating is directly adjacent the at least one of the first side and the opposing second side of the microporous substrate and the coating is directly adjacent at least one electrode or plate in a battery such as a lead acid battery.

[0032] In one aspect, alone or in combination with any previous aspect, at least one of the first side or the opposing second side comprises a flat sheet, ribs, protrusions, dimples, or combinations thereof. In one aspect, alone or in combination with any previous aspect, when present, the ribs or protrusions are continuous, discontinuous, longitudinally extending, machine direction (MD), transverse direction (TD), latitudinally extending, transverse, cross, mini, diagonally extending, angled, zig-zagged, wavy, or combinations thereof. In one aspect, alone or in combination with any previous aspect, the ribs are on the first side and the protrusions are on the opposing side. In one aspect, alone or in combination with any previous aspect, the at least one of the first side or the opposing second side ribs are a combination of continuous, broken, or angled ribs. In one aspect, alone or in combination with any previous aspect, the ribs that are on the first side are larger than the ribs on the opposing side. In one aspect, alone or in combination with any previous aspect, the ribs on at least one of the first and the opposing side are latitudinal, transverse, TD, or cross ribs.

[0033] In one aspect, alone or in combination with any previous aspect, the coating contours the ribs or protrusions and / or provides indentations or channels therein. In one aspect, alone or in combination with any previous aspect, the ribs or protrusions extend from a backweb and the coating at least covers or contours or covers the backweb between the ribs or protrusions.

[0034] In one aspect, alone or in combination with any previous aspect, the separator is at least partially ionically conductive when exposed to electrolyte or sulfuric acid ofSpecific Gravity of at least 1 .0.

[0035] In one aspect, alone or in combination with any previous aspect, the coating is an aqueous emulsion or slurry of at least the polymer binder and the siliceous material. In one aspect, alone or in combination with any previous aspect, the weight ratio of the polymeric binder to the siliceous material is from 1 :2 to 1 :10.

[0036] In one aspect, alone or in combination with any previous aspect, the coating comprises an emulsifier, an ionic surfactant, a cationic surfactant, additives, or combinations thereof. In one aspect, alone or in combination with any previous aspect, the emulsifier is at least one of alkyl benzene sulfonate, polyethylene glycol (PEG), polypropylene glycol (PPG), alkyl sulfate, polyoxyethylene alkyl ether, and alkyl sulfonate.

[0037] In one aspect, alone or in combination with any previous aspect, the polymeric binder is a non-elastomeric polymer.

[0038] In one aspect, alone or in combination with any previous aspect, the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, or blends or grafts thereof.

[0039] In one aspect, alone or in combination with any previous aspect, the cellulosic derivative is carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose.

[0040] In one aspect, alone or in combination with any previous aspect, the polymeric binder is a mixture of a non-elastomeric polymer or an elastomeric polymer and a cellulosic derivative. In one aspect, alone or in combination with any previous aspect, the polymeric binder is a mixture of an elastomeric polymer combined with a cellulosic derivative, or a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose. In one aspect, alone or in combination with any previous aspect, the polymeric binder is a mixture of a non-elastomeric polymer, siliceous material, and a cellulosic derivative in a weight ratio of from 1 :2:0.1 to 1 :10:0.5.

[0041] In one aspect, alone or in combination with any previous aspect, the polymeric binder is dried, cured or crosslinked.

[0042] In one aspect, alone or in combination with any previous aspect, the siliceous material is a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

[0043] In one aspect, alone or in combination with any previous aspect, the volume of the siliceous material in the coating when applied to the separator is configured to swell about 10 volume percent to about 70 volume percent when contacted with sulfuric acid. In one aspect, alone or in combination with any previous aspect, at least one of a thickness, a height, or a width of the coating when applied to the separator is configured to swell about 10 volume percent to about 70 volume percent when contacted with sulfuric acid.

[0044] In one aspect or example, a method of manufacturing a lead acid battery is provided, the method comprising filling the free lead acid battery with an electrolyte, the lead acid battery comprising a separator as described in any one of the previous aspect positioned between a positive and a negative electrode, sealing the filled lead acid battery, and providing a filled lead acid battery, where the filling is completed without the use of a vacuum.

[0045] In one aspect, alone or in combination with any previous aspect, the filling is completed in less than four minutes. In one aspect, alone or in combination with any previous aspect, the filling is completed in three minutes or less. In one aspect, the lead acid battery is a maintenance-free battery.

[0046] In one aspect or example, a method of reducing acid stratification within a lead acid battery is provided, the method comprising filling a lead acid battery with electrolyte, the maintenance-free lead acid battery comprising a positive and a negative electrode and a separator therebetween, the separator comprising a coating when applied to the separator comprising a polymeric binder and a siliceous material, introducing an electrolyte to the coating, swelling the siliceous material 10%% to 70% by volume so as to decrease a gap between the separator and at least one of the positive electrode and the negative electrode, and reducing acid stratification within the lead acid battery. In one aspect, the lead acid battery is a maintenance-free lead acid battery. In one aspect, alone or in combination with any previous aspect, the filling is completed without the use of a vacuum.

[0047] In one aspect, alone or in combination with any previous aspect, the lead acid battery is a maintenance free battery. In one aspect, alone or in combination with any previous aspect, the lead acid battery is a flooded lead battery or a valve-regulated leadacid (VRLA) battery, with or without an absorptive glass mat (AGM).

[0048] In one aspect, alone or in combination with any previous aspect, the separator is a coated substrate and the substrate is a polyolefin membrane, a filled polyolefin porous membrane, a silica filled polyolefin microporous membrane, a silica filled polyethylene microporous membrane, a ribbed silica filled polyethylene microporous membrane, a glass mat, a ribbed glass mat, an absorptive glass mat (AGM), a ribbed absorptive glass mat, a woven, a non-woven, a PVC membrane, a phenolic membrane, a cellulosic material or membrane, or combinations thereof. In one aspect, alone or in combination with any previous aspect, the polymeric binder is a non-elastomeric polymer. In one aspect, alone or in combination with any previous aspect, the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, an elastomeric polymer in combination with a cellulosic derivative, or blends or grafts thereof.

[0049] In one aspect, alone or in combination with any previous aspect, the filler is a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

[0050] In one aspect, alone or in combination with any previous aspect, the electrolyte is acid electrolyte.

[0051] In one aspect or example, a method of manufacturing a battery separator is provided, the method comprising introducing a coating to at least one surface of a microporous substrate, the coating comprising a mixture of a polymeric binder and a siliceous material, and drying, crosslinking or curing the coating.

[0052] In one aspect, prior to the introducing step, the microporous substrate is primed, flame treated, plasma treated, or contacted with an adhesion promoter. In one aspect, alone or in combination with any previous aspect, the coating is an aqueous emulsion, suspension, dispersion, or slurry of the polymeric binder and the siliceous material.

[0053] In one aspect, alone or in combination with any previous aspect, the aqueous emulsion or slurry comprises an emulsifier, an ionic surfactant, a cationic surfactant, or combinations thereof. In one aspect, alone or in combination with any previous aspect, the emulsifier is at least one of alkyl benzene sulfonate, polyethylene glycol (PEG), polypropylene glycol (PPG), alkyl sulfate, polyoxyethylene alkyl ether, and alkyl sulfonate.

[0054] In one aspect, alone or in combination with any previous aspect, the polymeric binder is a non-elastomeric polymer. In one aspect, alone or in combination with any previous aspect, the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, an elastomeric polymer in combination with a cellulosic derivative, or blends or grafts thereof. In one aspect, alone or in combination with any previous aspect, the cellulosic derivative is carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose.

[0055] In one aspect, alone or in combination with any previous aspect, the siliceous material is hydrophobic silica, fumed silica, precipitated silica, montmorillonite, chemically modified silica, or combinations thereof.

[0056] In one aspect, alone or in combination with any previous aspect, the siliceous material is present at 1 to 10 weight percent or 1 to 20 weight percent relative to the weight percent of the polymeric binder. In one aspect, alone or in combination with any previous aspect, the polymeric binder is an elastomeric polymer combined with a cellulosic derivative, or a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose, siliceous material, and a cellulosic derivative in a weight ratio of from 1 :2:0.1 to 1 :10:0.5.

[0057] In one aspect, alone or in combination with any previous aspect, the coating comprises a crosslinking agent. In one aspect, alone or in combination with any previous aspect, during the drying or curing step, the coating is cross-linked.

[0058] In one aspect, alone or in combination with any previous aspect, the processing aids comprise one or more of emulsifiers, surfactants, anti-foaming agents, adhesion promoters, antioxidants, UV stabilizers, curing aids, and crosslinking agents.

[0059] In one aspect, alone or in combination with any previous aspect, prior to the introducing step, embossing the microporous substrate on the at least one surface or on both surfaces. In one aspect, alone or in combination with any previous aspect, prior to the introducing step, embossing the microporous substrate on both surfaces with the same or different profile or pattern. In one aspect, alone or in combination with any previous aspect, prior to the introducing step, embossing the microporous substrate on both surfaces with a flat sheet or the same or different pattern of ribs, protrusions, dimples, or combinations thereof.

[0060] In one aspect, alone or in combination with any previous aspect, the ribs or protrusions are continuous, discontinuous, longitudinally extending, latitudinally extending, diagonally extending, or combinations thereof.

[0061] In one aspect, alone or in combination with any previous aspect, the ribs or protrusions extend from a backweb and the coating at least covers the backweb between the ribs or protrusions.

[0062] In one aspect, alone or in combination with any previous aspect, the method further comprising shaping the separator to receive an electrode of a battery.

[0063] In another aspect or example, a coating formulation for a battery separator is provided, the coating formulation comprising a polymeric binder, an inorganic filler, and a remainder of aqueous media and processing aids.

[0064] In one aspect, alone or in combination with any previous aspect, the polymeric binder is a non-elastomeric polymer. In one aspect, alone or in combination with any previous aspect, the polymeric binder is an acrylate, a methacrylate, a styrene, a polyurethane, a polyurethane-urea, an elastomeric polymer combined with a cellulosic derivative, or a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose, or blends or grafts thereof.

[0065] In one aspect, alone or in combination with any previous aspect, the inorganic filler is a siliceous material. In one aspect, alone or in combination with any previous aspect, the siliceous material is at least one of a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

[0066] In one aspect, alone or in combination with any previous aspect, the inorganic filler is present at 1 to 10 weight percent relative to the weight percent of the polymeric binder.

[0067] In one aspect, alone or in combination with any previous aspect, the processing aids comprise one or more of emulsifiers, surfactants, anti-foaming agents, adhesion promoters, antioxidants, UV stabilizers, curing aids, and crosslinking agents. In one aspect, alone or in combination with any previous aspect, the coating formulation is an aqueous emulsion, dispersion, suspension, or slurry.

[0068] In another example, a system is provided, the system comprising at least onebattery cell comprising an electrode plate, a separator pocketing the electrode plate, or adjacent the electrode plate; the separator comprising a coating, the coating comprising a mixture of a polymeric binder and inorganic filler; wherein the inorganic filler is configured to swell upon contact with acid. The system provides performance of at least 80 percent of that of an AGM battery or Gel battery without the separator. The separator provides at least 66 weight percent absorption of acidic electrolyte after a Rupture Test in accordance with, Section 9.0 of the Battery Council International “BCI Specification For ‘Non-Spillable Certification’ Valve Regulated Lead-Acid (VRLA) Batteries” (BCS-21 ) test protocol.

[0069] In one aspect, the polymeric binder is a non-elastomeric polymer. In one aspect, alone or in combination with any previous aspect, the polymeric binder is an acrylate, a methacrylate, a styrene, a polyurethane, a polyurethane-urea, a cellulosic derivative, an elastomeric polymer in combination with a cellulosic derivative, or blends or grafts thereof.

[0070] In one aspect, alone or in combination with any previous aspect, the inorganic filler is a siliceous material. In one aspect, alone or in combination with any previous aspect, the siliceous material is at least one of a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, a mixture of two or more thereof, or a combination thereof. In one aspect, alone or in combination with any previous aspect, the inorganic filler is present at 1 to 10 weight percent relative to the weight percent of the polymeric binder.

[0071] In another aspect or example, an internal combustion engine (ICE), hybrid, or electric vehicle comprising at least one battery is provided, the at least one battery comprising two or more electrodes, a separator positioned between the two or more electrodes, the separator coated with a mixture of a polymeric binder and a siliceous material an electrolyte a least partially absorbed by the siliceous material.

[0072] In one aspect, alone or in combination with any previous aspect, the separator comprises a polyolefin membrane, a filled polyolefin porous membrane, a glass mat, an absorptive glass mat (AGM), a woven, a non-woven, a PVC membrane, a phenolic membrane, or combinations thereof.

[0073] In one aspect, alone or in combination with any previous aspect, in a preferred example a VRLA (Valve Regulated Lead Acid) battery may comprise a compositeseparator that includes an absorptive glassmat (AGM) separator and a polyolefin membrane with mini-ribs or cross-ribs coated with a mixture of a polymeric binder and a siliceous material positioned in a reverse orientation or positioned up next to the PAM.

[0074] In one aspect, alone or in combination with any previous aspect, the polymeric binder comprises a non-elastomeric polymer. In one aspect, alone or in combination with any previous aspect, the siliceous material comprises hydrophobic silica, fumed silica, precipitated silica, montmorillonite, chemically modified silica, or combination thereof.

[0075] The above summary is provided merely for purposes of summarizing some examples to provide a basic understanding of some aspects of the present disclosure. Accordingly, it will be appreciated that the above-described examples are merely illustrative and should not be construed to narrow the scope or spirit of the disclosure in any way. It will be appreciated that the scope of the present disclosure encompasses many potential examples in addition to those here summarized, some of which will be further described below.BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Having thus described examples of the disclosure in general terms, reference will now be made to the accompanying drawings.

[0077] FIG. 1A illustrates a front view of a separator, in accordance with examples of the disclosure;

[0078] FIG. 1 B illustrates a front view of a separator, in accordance with examples of the disclosure;

[0079] FIG. 2 illustrates a front view of a separator, in accordance with examples of the disclosure;

[0080] FIG. 3 illustrates a front view, top view, and side view of a separator, in accordance with examples of the disclosure;

[0081] FIG. 4 illustrates a front view, top view, and side view of a separator, in accordance with examples of the disclosure;

[0082] FIG. 5 illustrates a front view of a separator, in accordance with examples of the disclosure;

[0083] FIG. 6 illustrates a front view of a separator, in accordance with examples of the disclosure;

[0084] FIG 7 is light microscope cross-sectional images showing evidence of swelling and homogenous plate pressure with the use of the examples of the separators of the disclosure. The EFS-19X has the cross rib or mini rib side (the X side) in intimate contact with the PAM (Positive Active Material). The EFS-19X has the major rib side (the 19 side) in intimate contact with the PAM (Positive Active Material).

[0085] FIG. 8 illustrates cross section microscope images of a coated separator, in accordance with examples of the separator of the disclosure;

[0086] FIG. 9 illustrates side views of a coated separator between electrodes, in accordance with examples of the separator of the disclosure;

[0087] FIG. 10 illustrates side views of a coated separator between electrodes, in accordance with examples of the separator of the disclosure;

[0088] FIG. 11 illustrates side views of a control cell and cell containing separators between electrodes, in accordance with examples of the separator of the disclosure;

[0089] FIG. 12 illustrates side views of a control and coated separators between electrodes, in accordance with examples of the separator of the disclosure;

[0090] FIG. 13 illustrates side views of a control and coated separators between electrodes, in accordance with examples of the separator of the disclosure;

[0091] FIG. 14 illustrates a graph of data obtained using a hydrometer which plots change in specific gravity to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure;

[0092] FIG. 15 illustrates a graph of data obtained using a voltmeter which plots average EoD (End of Discharge) voltage to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure, wherein the top trace across is that of the AGM, moving downward the next trace across is the EFS-19X(+); moving downward the next trace across is the EFS-19X(-); moving downward the next (bottom) trace across is the EFS-19X(Ctrl, no coating);

[0093] FIG. 16 illustrates a graph of data obtained using a voltmeter which plots terminal discharge voltage to number of cycles, in accordance with examples of the separator of the disclosure with typical rib orientation; wherein wherein the top trace across is that of the _P-120-19X-n1 , moving downward the next trace across is the _P- 270-19X-n1 ; moving downward the next trace across is the P-120-19X-n2; movingdownward the next trace across is the _P-120-19X-3n; moving downward the next trace across is the _N-110-19X-n1 ; moving downward the next trace across is the _N-240-19X- n1 ; moving downward the next trace across is the _N-240-19X-n2; moving downward the next trace across is the _P-270-19X-n2; moving downward the next trace across is the _P-270-19X-n3; moving downward the next trace across is the _N-240-19X-n3; moving downward the next trace across is the Control 1_(no coating); moving downward the next trace across is the _N-110-19X-n2; moving downward the next trace across is the N-110-19X-n3; moving downward the next trace across is the Control 2 (no coating); moving downward the next (bottom) trace across is the Control 3 (no coating);

[0094] FIG. 17 illustrates a graph of data obtained using a hydrometer which plots the difference in specific gravity between top and bottom, in accordance with examples of the separator of the disclosure;

[0095] FIG. 18 illustrates an image of a control sample separator after a cycle life test;

[0096] FIG. 19 illustrates an image of a separator after a cycle life test, in accordance with examples of the separator of the disclosure;

[0097] FIG. 20 illustrates a graph of data obtained using a voltmeter which plots average voltage to number of cycles, in accordance with control and coated examples of the disclosed separator, wherein the red dotted lines referred to are the two horizontal dashed lines, wherein the trace that crosses the lower dashed line at the position closest the y-axis is the [EFS-19X]; wherein the trace that crosses the lower dashed line at the position next closest the y-axis is the EFS-19X; wherein the trace that meets the upper dashed line at the position next closest the y-axis is the EFS-19X(+); wherein the trace that meets the upper dashed line at the position next closest the y-axis is the EFS- 19X(-); wherein the trace that meets the upper dashed line at the position next closest the y-axis is the [EFS-19X(-)]; wherein the trace that runs across without meeting the upper dashed line is the [EFS-19X(+)].

[0098] FIG. 21 illustrates side views of separators between electrodes, in accordance with examples of the separator of the disclosure;

[0099] FIG. 22 illustrates a graph of data obtained using a voltmeter which plots average discharge voltage to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure;

[0100] FIG. 23 illustrates a graph of data of oxidation lifetime, in accordance with control and coated examples of the disclosed separator;

[0101] FIG. 24A illustrates an image of a control sample separator after an oxidation lifetime test;

[0102] FIG. 24B illustrates an image of a separator after an oxidation lifetime test, in accordance with examples of the separator of the disclosure;

[0103] FIG. 25 illustrates a graph of data obtained using a voltmeter which plots discharge voltage to step time, in accordance with AGM, control and coated examples of the separator of the disclosure, wherein the traces are labelled using arrows and also are color coded as per the inset scheme;

[0104] FIG. 26 illustrates a graph of data obtained using a voltmeter which plots average discharge capacity to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure;

[0105] FIG. 27 illustrates a graph of data obtained using a voltmeter which plots discharge capacity to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure; wherein the AGM values are those with the lowest y-axis values at positions 1 , 2, 3, 4 and 5 on the x-axis; wherein the U250X - LH OOum values are those with the highest y-axis values at positions 1 , 2, 3 and 4 on the x-axis; wherein the U250X - D100um values are those with the second highest y-axis values at positions 1 , 2, 3 and 4 on the x-axis; wherein the LI250X - Uncoat values are those with the second lowest y-axis values at positions 1 , 2, 3 and 4 on the x-axis;

[0106] FIG. 28 illustrates timed images of the filling of a battery, in accordance with examples of the separator of the disclosure;

[0107] FIG. 29 illustrates timed images of the filling of a battery having an absorbed glass mat;

[0108] FIG. 30 illustrates a graph of data obtained using a voltmeter which plots discharge voltage to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure wherein the top trace across is that of the AGM, moving downward the next (middle) trace across is the 19X- New inventive separator (+); ; moving downward the next (bottom) trace across is the 19X - Control ;

[0109] FIG. 31 illustrates a graph of data obtained using a hydrometer which plots the difference in specific gravity between top and bottom to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure, wherein the top trace across is that of the 19X-Uncoat, moving downward the next (middle) trace across is the 19X- New inventive separator; moving downward the next (bottom) trace across is the AGM;

[0110] FIG. 32 illustrates a graph of data obtained using a hydrometer which plots change in specific gravity to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure;

[0111] FIG. 33 illustrates a graph of data obtained using a voltmeter which plots end of discharge voltage to number of cycles, in accordance with the examples of the separator of FIG. 32 wherein the top trace across is that of the AGM, moving downward the next trace across is the EFS-19X(+); moving downward the next trace across is the EFS-19X(- ); moving downward the next (bottom) trace across is the EFS-19X(Ctrl, no coating);

[0112] FIG. 34 illustrates a graph of data obtained using a voltmeter which plots end of discharge voltage to number of cycles, in accordance with AGM, control and coated examples of the separator of the disclosure wherein, the trace that has the highest values on the y-axis between 100 and 400 cycles on the x-axis is that of the AGM (30% Compression), moving downward the trace that has the second highest values on the y- axis between 100 and 400 cycles on the x-axis is that of the LI250X Single side coated (5% Compression); moving downward the trace that has the third highest values on the y-axis between 100 and 400 cycles on the x-axis is that of the U250X Double side coated (5% Compression); the trace that has the fourth highest values (lowest values) on the y- axis between 100 and 400 cycles on the x-axis is that of the U250X (5% Compression);

[0113] FIG. 35 illustrates a graph of the stages of a charge test protocol, in accordance with examples of the separator of the disclosure;

[0114] FIG. 36 illustrates cross-sectional views of a separator, obtained by a Hirox Microscope, after the charge test protocol of FIG. 35, in accordance with control and coated examples of the separator of the disclosure.

[0115] FIG. 37 illustrates a graph of data obtained using a voltmeter which plots charge voltage to step time, in accordance with AGM, control and coated examples of the separator of the disclosure, wherein the traces are labelled using arrows and also are color coded as per the inset scheme;

[0116] FIG. 38 illustrates a graph of data obtained using a voltmeter which plots charge current to step time, in accordance with AGM, control and coated examples of the separator of the disclosure, wherein the traces are labelled using arrows and also are color coded as per the inset scheme;

[0117] FIG. 39 illustrates a graph of data which plots puncture strength, in accordance with examples of the separator of the disclosure, wherein for each of llncoat and Binder A to Binder J the results are given in pairs with the Before value on the left and the After value on the right;

[0118] FIG. 40 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.1 , in accordance with examples of the separator of the disclosure;

[0119] FIG. 41 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.1 , in accordance with examples of the separator of the disclosure;

[0120] FIG. 42 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.2, in accordance with examples of the separator of the disclosure;

[0121] FIG. 43 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.2, in accordance with examples of the separator of the disclosure;

[0122] FIG. 44 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.3, in accordance with examples of the separator of the disclosure;

[0123] FIG. 45 illustrates a cross-sectional view of a separator, obtained by a Hirox Microscope, after exposure to an acid with a specific gravity of 1.3, in accordance with examples of the separator of the disclosure;

[0124] FIG. 46 illustrates a cross-sectional view of a first side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0125] FIG. 47 illustrates a cross-sectional view of a first side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0126] FIG. 48 illustrates a cross-sectional view of first side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0127] FIG. 49 illustrates a cross-sectional view of a second side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0128] FIG. 50 illustrates a cross-sectional view of a second side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0129] FIG. 51 illustrates a cross-sectional view of second side of a separator, obtained by a Hirox Microscope, after prolonged exposure to an acid with a specific gravity of 1 .28, in accordance with examples of the separator of the disclosure;

[0130] FIG. 52 is a schematic drawing showing two sides of a ribbed separator according to some embodiments described herein.

[0131] FIG. 53 is a schematic drawing showing two sides of a ribbed separator according to some embodiments described herein;

[0132] FIG. 54 is a graph depicting 12V Commercial Group Size 65 Standard SLI maintenance free flooded Battery results VW 17.5% PSoC Cycle Life Performance with a 500% increase in cycles under zero compression using a reverse separator orientation;

[0133] FIG. 55 is a graph depicting 12V Group Size 48Standard commercial SLI maintenance-free Flooded Battery Results EN 50% DOD Cycle Life Performance using a “Snug-fit” Compression (1 -5% compression) and a reverse separator Orientation;

[0134] FIG. 56 is a bar graph representing the change in specific gravity of the acid for the 12V Group Standard Size 65 SLI Flooded battery 17.5% PSoC ASpG at the End ofLife showing the PE + stratosphere reduces acid stratification by at least 50%compared to PE without Stratosphere; and

[0135] FIG 57 is graph showing 2V VRLA cells VW 17.5% PSoC Life Performance results in accordance with the examples of the separators of the disclosure. Surpr Surprisingly, the AGMe SS 5% compression outperforms the 30% Compression AGM Battery. The possibly preferred inventive AGMe SS 5% Compression may perform comparable to the 30% AGM "Gold Standard" but with less compression which is a manufacturing advantage. At least certain possibly preferred inventive AGMe SS at less than 30% Compression may perform comparable to the 30% AGM "Gold Standard" but with less compression which is a manufacturing advantage.DETAILED DESCRIPTION

[0136] In accordance with at least certain embodiments, aspects or objects of the present invention or disclosure, there are disclosed or provided novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and / or batteries incorporating the same.

[0137] In accordance with at least selected embodiments, aspects or objects of the present invention or disclosure, there are disclosed or provided a coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane is provided comprising a microporous substrate; and a coating on one or both sides of the microporous substrate. The coating comprises a polymeric binder and inorganic filler or siliceous material. In some examples, the separator is coated on one or both sides of the microporous substrate or membrane, wherein the coating comprises a polymeric binder, siliceous material, and carboxymethyl cellulose (CMC). In some examples, the microporous substrate may be a flat sheet or a ribbed microporous substrate comprising polyethylene.

[0138] Disclosed herein is a coated battery separator that adeptly controls electrolyte stratification by volumetrically swelling into the void space between electrodes at least partially absorbing and immobilizing an electrolyte. The presently disclosed coated battery separator at least partially retards stratification and providing improved uniform electrolyte concentration, improved ion transport and improved reliability of charge-state communication with battery management systems. The presently disclosed coated battery separator results in >2X longer cycle life in Partial State of Charge (PSoC) applications, while maintaining affordability of FLA batteries compared to AGM batteries. Furthermore, for AGM batteries, the presently disclosed coated separator technology can replace AGM separator, decreasing filling and formation times, negating the need for vacuum systems, high battery compression (>5%), or expensive VRLA manufacturing processes.

[0139] The presently disclosed coated battery separator consolidates the best aspects of AGM Valve-Regulated Lead-Acid Batteries (AGM VRLA), Gel VRLA and FLA battery separator technologies, providing a stable voltage consistent with typical AGM VRLA, a cycle life consistent with typical Gel VRLA, and the lower cost and ease of manufacturing associated with FLA batteries. The presently disclosed coated battery separator represents advancement and evolution in the field of lead-acid batteries.

[0140] In accordance with at least certain aspects, objects or embodiments, a coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane is provided comprising a microporous substrate; and a coating on one or both sides of the microporous substrate. The coating comprises a polymeric binder and inorganic filler or siliceous material. In some examples, the separator is coated on one or both sides of the microporous substrate or membrane, wherein the coating comprises a polymeric binder, siliceous material, and carboxymethyl cellulose (CMC). In some examples, the microporous substrate may be a ribbed microporous substrate comprising polyethylene.

[0141] Disclosed herein are improved battery separators for use in flooded lead acid batteries, enhanced flooded lead acid batteries, and the like that are prone to having acid stratification issues. Examples of the present disclosure now may be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all,examples are shown. Indeed, the disclosure may be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these examples are provided so that this disclosure may satisfy applicable legal requirements. Like numbers refer to like elements throughout. Where possible, any terms expressed in the singular form herein are meant to also include the plural form and vice versa, unless explicitly stated otherwise. Also, as used herein, the term “a” and / or “an” shall mean “one or more,” even though the phrase “one or more” is also used herein. Furthermore, when it is said herein that something is “based on” something else, it may be based on one or more other things as well. In other words, unless expressly indicated otherwise, as used herein “based on” means “based at least in part on” or “based at least partially on.”

[0142] Additionally, certain terminology is used herein for convenience only and is not to be interpreted as a limitation on the examples described. For example, the words “top,” “bottom,” “upper,” “lower,” “left,” “right,” “horizontal,” “vertical,” “upward,” and “downward” merely describe the configurations as depicted in the figures. Indeed, the referenced components in the figures may be oriented in any direction, unless specified otherwise, the configurative terminology used herein should be understood as encompassing such variations. If not specified, these terms can be related to the presently disclosed coated battery separator orientation when it is incorporated in a battery configuration and used as intended, for example, relative to a FLA battery’s orientation when properly installed in a vehicle.Batteries and Coated Separators

[0143] In some examples herein, a battery comprises at least one cell, each cell having a positive and negative electrode, and an improved coated separator as described hereinabove, between the positive and negative electrode. In some examples herein, a VRLA battery comprises a positive and negative electrode, and both an AGM VRLA separator (i.e., an absorbent glass mat (AGM) separator), and an improved coated separator as described hereinabove, between the positive and negative electrode.

[0144] Examples of flooded lead acid batteries that may have acid stratification issues include, but are not limited to, an enhanced flooded battery (EFB), a starting, lighting, igniting (SLI) battery, and the like. The improved battery separator described herein enables FLA batteries (hereinafter also referred to a FLB) to be used as an auxiliarybattery in a vehicle or other device. As described above, acid stratification in auxiliary batteries is potentially worse than in other types of batteries (e.g., primary batteries), and use of FLA batteries as auxiliary batteries has been difficult prior to the present inventive improved coated separator.Coated Separator Configuration

[0145] In one example, the presently disclosed coated separator comprises a substrate and a coating on the substrate or substrate (herein used interchangeably). In one example, the substrate is generally flat and is essentially continuous in length with an essentially constant width having opposing major surfaces (or sides) separated by an essentially constant thickness such that the substrate can be provided in a roll form. In one example, the substrate is generally flat on one side of the width. In one example, the substrate is generally flat on one major surface or side and has structural features on another side. In one example, the substrate has structural features on both major surfaces and sides, the structural feature being the same or different. In one example, the substrate has structural features on both major surfaces and sides, the structural feature being different in shape, height, and / or arrangement. As used herein, the height of the structural features are measured from the major surface they project from, also referred to as a “backweb.” In one example, the substrate is porous so as to allow ions to diffuse and or migrate therethrough. In one example, the substrate is microporous so as to allow ions to diffuse and or migrate therethrough. The improved coated separator described herein may comprise ribs, protrusions and / or dimples that extend parallel to a top and a bottom of the battery. Benefits of this arrangement may include, reducing compressibility of the separator, further benefits include reducing or even eliminating acid stratification issues. Various modifications and structures of the presently disclosed substrate of the coated separator are further disclosed and described below.

[0146] Referring now to FIGS. 1A-1 B, several examples of ribbed separators with different rib profiles are depicted. It may be preferred that the shown ribs are positive. The angled rib pattern of FIGS. 1A-1 B may be a possibly preferred Daramic® RipTide™ acid mixing rib profile that can help reduce or eliminate acid stratification in certain batteries The FIG. 1 B profile may be a diagonal offset rib pattern. The negative face could have no ribs (smooth), the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs or NCRs,diagonal ribs, or combinations thereof. Also, referring to FIGS. 52 and 53, these show a two-sided view of a ribbed separator according to some embodiments described herein. The dashed rectangles, which represent nubs, dimples, or protrusions. The dashed lines are meant to indicate their presence on the opposite side of the membrane from the longitudinal continuous ribs. Spacing between the longitudinal continuous ribs is indicated in the FIGS. For example, spacing in FIG. 52 is 3.6 mm, and spacing in FIG. 53 is 7.2 mm. Spacing between longitudinal continuous ribs is equidistant.

[0147] With reference now to FIG. 2, an exemplary substrate 100 has a top edge 101 , a bottom edge 103, lateral side edges 105 a, 105 b, a machine direction (MD) and a cross-machine direction (CMD). An exemplary separator may be provided with a backweb 102 of a porous or microporous substrate, and a series of major or positive ribs 104 extending therefrom and preferably disposed along the longitudinal or MD of the separator. As used herein, a “substrate” may refer to the separator base or backweb on which a coating is applied, discussed further below.

[0148] As shown, the ribs 104 are serrated. However, the ribs 104 may be solid ribs, grooves, textured areas, serrations or serrated ribs, solid ribs, battlements or battlemented ribs, broken ribs, angled ribs, linear ribs, or curved or sinusoidal ribs, zigzag ribs, embossments, dimples, and / or the like extending into or from the backweb 102, or any combination thereof. In some examples, positive ribs may be at an angle between greater than 0° and less than 180° or greater than 180° and less than 360°, and negative or negative cross-ribs may be on a second surface of the microporous substrate and disposed generally parallel to a top edge or a CMD of the separator.

[0149] Some examples place the separator in a battery (not shown) with the ribs 104 facing a positive electrode (not shown), but this is not necessary. Should the ribs 104 face a positive electrode, they may be known as positive ribs. In addition ribs (not shown) extending from the opposite side of the microporous substrate will face a negative electrode (not shown) and may be disposed longitudinally in the MD or transversely in the CMD. If disposed along the CMD they are generally known as “cross-ribs” and as discussed hereinafter will be referred to as “negative cross-ribs” or “NCR” or “NCRs.” The substrate 100 will typically be placed in a battery positioning the negative cross-ribs toward the negative electrode, however this is not necessary. In addition and ascompared to the positive ribs, the negative ribs may be the same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs, NCRs, diagonal ribs, or combinations thereof. Furthermore, the negative and / or the positive surface of the separator may be in whole or in part void of any ribs and thus be smooth or flat on one or both sides of the separator.Manufacture / Thickness

[0150] In some examples, the microporous substrate can have a backweb thickness from about 50 pm-1 .0 mm, and at least about 50 pm, at least about 75 pm, at least about 100 pm, at least about 125 pm, at least about 150 pm, at least about 175 pm, at least about 200 pm, at least about 225 pm, at least about 250 pm, at least about 275 pm, at least about 300 pm, at least about 325 pm, at least about 350 pm, at least about 375 pm, at least about 400 pm, at least about 425 pm, at least about 450 pm, at least about 475 pm, or at least about 500 pm (though in certain examples, a very thin flat backweb thickness of 50 pm is provided, for example, between 10 pm and 50 pm thick). In certain examples, the backweb thickness may be less than or equal to about 125 pm±35 pm.

[0151] The overall thickness of the battery separators described herein is calculated by adding the backweb thickness, the height of the tallest rib on a first side, and the height of a tallest rib on a second side. It is measured using BCI method (BCIS-03B Overall Thickness Section16). In one example, the overall thickness is about equal to the required plate spacing in the battery. Overall thickness ranges from about 200 microns to about 4,000 microns, 500 microns to about 1 ,100 microns, from 500 microns to 1 ,000 microns, from 500 microns to 900 microns, from 500 microns to 800 microns, from 500 microns to 700 microns, or from 500 microns to 600 microns. In an auxiliary battery, plate spacing is typically between about 600 microns and 1 ,000 microns, so for this application overall thickness should fall within this range.Separator Ribs

[0152] In some examples, one or more surface or face of the microporous substrate may have ribs, protrusions, or both ribs and protrusions. In examples where ribs are present, the ribs do not have any particular structure but are at least one of the following: continuous ribs, discontinuous ribs, longitudinally extending ribs, latitudinally extending ribs, diagonally extending ribs, integral ribs, non-integral ribs, mini ribs, and combinations thereof. For example, the ribs could be discontinuous and diagonally extending ribs.Protrusions are not ribs but are included. One example of protrusions may include, but is not limited to, dimples. When ribs, protrusions, or ribs and protrusions are formed on both faces of the substrate, the types of ribs, protrusions, or ribs and protrusions formed on each face or surface are the same or different. For example, latitudinally extending ribs are formed on one face or surface of the substrate or membrane and longitudinally extending ribs are formed on the other face or surface. In some examples, latitudinally extending ribs are formed on a positive face of the microporous substrate, and longitudinally extending ribs are formed on a negative face (i.e. , negative cross ribs).

[0153] In some examples when ribs, protrusions, or ribs and protrusions are formed on a surface of the substrate, one or more edge regions of the substrate may not include ribs, protrusions, or ribs and protrusions or the one or more edge regions may only include mini ribs, mini protrusions, or mini ribs and protrusions. A mini rib or mini protrusion may have a maximum height from the face of the substrate to the highest point of the rib or protrusion that is at most 100 to at most 250 microns from the face of the substrate. In some examples, the maximum height is at most 25 microns, at most 50 microns, at most 75 microns, at most 100 microns, at most 125 microns, at most 150 microns, at most 175 microns, at most 200 microns, or at most 225 microns.

[0154] Indeed, the ribs may be continuous, discontinuous, solid, porous, non-porous, on the positive side, on the negative side, on both sides, mini ribs or cross mini ribs on the negative side, and / or the like. The ribs may be serrated in certain examples (such as serrated positive ribs, negative ribs, or both). The serrations or serrated ribs may have an average tip length of from about 0.05 mm to about 1 mm. For example, the average tip length may be greater than or equal to 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to 1 .0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0155] The serrations or serrated ribs may have an average base length of from about 0.05 mm to about 1 mm. For example, the average base length may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1 .0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 04 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0156] If serrations or serrated ribs are present, they may have an average height of from about 0.05 mm to about 4 mm. For example, the average height may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1 .0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm. For examples in which the serration height is the same as the rib height, the serrated ribs may also be referred to as protrusions. Such ranges may apply to separators for industrial traction-type start / stop batteries, where the total thickness of the coated separator 724 may typically be about 1 mm to about 4 mm, as well as automotive start / stop batteries, where the total thickness of the coated separator 724 may be a little less (e.g., typically about 0.3 mm to about 1 mm).

[0157] The serrations or serrated ribs may have an average center-to-center pitch within a column in the machine direction of from about 0.1 mm to about 50 mm. For example, the average center-to-center pitch may be greater than or equal to about 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1 .5 mm; and / or less than or equal to about 1 .5 mm, 1 .25 mm, 1 .0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm. In addition, adjacent columns of serrations or serrated ribs may be identically disposed at the same position in a machine direction or offset. In an offset configuration, adjacent serrations or serrated ribs are disposed at different positions in the machine direction. FIG. 1A shows serrated ribs disposed in an offset configuration.

[0158] The serrations or serrated ribs can have an average height to base width ratio of from about 0.1 :1 to about 500:1. For example, the average height to base width ratio may be greater than or equal to about 0.1 : 1 , 25: 1 , 50: 1 , 100: 1 , 150: 1 , 200: 1 , 250: 1 , 300: 1 , 350:1 , or 450:1 ; and / or less than or equal to about 500:1 , 450:1 , 400:1 , 350:1 , 300:1 , 250:1 , 200:1 , 150:1 , 100:1 , 50:1 , or 25:1.

[0159] The serrations or serrated ribs can have average base width to tip width ratio of from about 1000:1 to about 0.1 :1. For example, the average base width to tip width ratio may be greater than or equal to about 0.1 :1 , 1 :1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 , 10:1 , 15:1 , 20:1 , 25:1 , 50:1 , 100:1 , 150:1 , 200:1 , 250:1 , 300:1 , 350:1 , 450:1 , 500:1 , 550:1 , 600:1 , 650:1 , 700:1 , 750:1 , 800:1 , 850:1 , 900:1 , 950:1 , and / or less than or equal to about1000:1 , 950:1 , 900:1 , 850:1 , 800:1 , 750:1 , 700:1 , 650:1 , 600:1 , 550:1 , 500:1 , 450:1 , 400:1 , 350:1 , 300:1 , 250:1 , 200:1 , 150:1 , 100:1 , 50:1 , 25:1 , 20:1 , 15:1 , 10:1 , 9:1 , 8:1 , 7:1 , 6:1 , 5:1 , 4:1 , 3:1 , 2:1 , or 1 :1 .

[0160] In some examples, the coated separator 724 can feature a combination of solid ribs, serrations or serrated ribs, battlemented ribs, dimples, or combinations thereof. For instance, a coated separator 724 can have a series of serrated ribs running top to bottom along the coated separator 724, and a second series of serrated ribs running horizontally along the coated separator 724. In other examples, the coated separator 724 can have an alternating sequence of solid ribs, serrated ribs, dimples, continuous, interrupted, or broken solid ribs, or combinations thereof.

[0161] In some selected examples, the microporous substrate can have negative longitudinal or cross-ribs on the opposite face of the membrane as the protrusions. The negative or back rib may be parallel to the top edge of the coated separator 724, or may be disposed at an angle thereto. For instance, the cross ribs may be oriented about 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15° or 5° relative to the top edge. The cross-ribs may be oriented about 90-60°, 60-30°, 60-45°, 45-30°, or 30-0° relative to the top edge. Typically the cross-ribs are mini ribs on the face of the membrane facing the negative electrode. As shown in FIG. 36, certain new profiles can have tall cross ribs facing the positive electrode. In some examples of the present disclosure, the ribbed membrane can have a transverse cross-rib height HNCR (height of negative cross rib) of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some examples of the present disclosure, the ribbed membrane can have a transverse cross-rib height of no greater than about 1 .0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm or 0.05 mm.

[0162] In some examples of the present disclosure, the ribbed membrane can have a transverse cross-rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 03 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some examples of the present disclosure, the ribbed membrane can have a transverse cross-rib width of no greater than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm or 0.05 mm.

[0163] In certain selected examples the microporous substrate can have a transverse cross-rib height of about 0.10-0.15 mm, and a longitudinal rib height of about 0.10-0.15 mm. In some examples, the microporous substrate can have a transverse cross-rib height of about 0.10-0.125 mm, and a longitudinal rib height of about 0.10-0.125 mm.

[0164] Such negative cross-ribs may be smaller and more closely spaced than the positive ribs. The positive ribs 104 may have a height of between 8 pm to 1 mm and may be spaced 1 pm to 20 mm apart, while the preferred backweb thickness of the microporous polyolefin microporous substrate (not including the ribs or embossments) may be about 50 pm to about 500 pm (for instance, in certain examples, less than or equal to about 125 pm). For example, the ribs may be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, and in similar increments up to 20 mm apart.

[0165] The negative cross-ribs may have a height of between about 25 pm to about 100 pm, and preferably about 50 pm-75 pm, but may be as small as 25 pm. In some instances, the NCRs may be about 25 pm to about 250 pm, or preferably be about 50 pm-125 pm, or preferably between about 50 pm-75 pm.Envelope / Form

[0166] The substrate 100 may be provided as a flat sheet, a cut piece, a leaf or leaves, a wrap, a V or U, a sleeve, a gauntlet, an envelope or pocket, or a hybrid envelope or pocket with slits or openings as the separator substrate or membrane. An exemplary envelope separator may envelope a positive electrode (“positive enveloping separator” or “P-wrapped”), such that the coated separator 724 has two interior sides facing the positive electrode(s) and two exterior sides facing adjacent negative electrode(s). Alternatively, another exemplary envelope separator may envelope a negative electrode (“negative enveloping separator” or “N-wrapped”), such that the coated separator 724 has two interior sides facing the negative electrode(s) and two exterior sides facing adjacent positive electrode(s). In such enveloped separators, the bottom edge 103, as shown in FIG. 2, may be a folded or a sealed crease edge. Further, the lateral edges 105a, 105b may be continuously or intermittently sealed seam edges. The edges may be bonded or sealed by adhesive, heat, ultrasonic welding, and / or the like, or any combination thereof.

[0167] Certain exemplary separators may be processed to form hybrid envelopes. The hybrid envelope may be provided by forming one or more slits or openings before, during or after, folding the coated separator 724 sheet in half and bonding edges of the coated separator 724 sheet together so as to form an envelope. The length of the openings may be at least 1 / 50th, 1 / 25th, 1 / 20th, 1 / 15th, 1 / 1 Oth, %th, Vsth,1 / 4th, or1 / 3rd the length of the entire side or bottom edge. The length of the openings may be 1 / 50th to 34rd, 1 / 25th to rd, 1 / 20th to %rd. 1 / 20th to 34th, 1 / 15th to 34th, 1 / 15th to Vsth or 1 / 1 Oth to Vsth the length of the entire bottom edge. The hybrid envelope can have 1-5, 1 -4, 2-4, 2-3 or 2 openings, which may or may not be equally disposed along the length of the side or bottom edge. It is preferred that no opening is in the corner of the envelope. The slits may be cut after the coated separator 724 has been folded and sealed to give an envelope, or the slits may be formed prior to shaping the microporous substrate into the envelope (or pocket, sleeve, wrap, etc.)

[0168] Some other exemplary examples of coated separator 724 assembly configurations include: the ribs 104 facing a positive electrode; the ribs 104 facing a 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 enveloped or sleeved, and any combination thereof.Substrate Composition

[0169] In certain examples, the improved coated separator 724 includes a microporous substrate made of: a natural or synthetic base material and can further include one or more of a processing plasticizer; a filler; natural or synthetic rubber(s) or latex, and one or more other additives, and / or the like.

[0170] In certain examples, exemplary natural or synthetic base materials may include: polymers; thermoplastic polymers; phenolic resins; natural or synthetic rubbers; synthetic wood pulp; lignins; glass fibers; synthetic fibers; cellulosic fibers; and any combination thereof. In one example, an exemplary substrate of the coated separator 724 is a microporous substrate made from thermoplastic polymers. Exemplary thermoplastic polymers may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead acid batteries. In certain preferred examples, exemplary thermoplastic polymers may include polyvinyls and polyolefins. In certain examples, the polyvinyls mayinclude, for example, polyvinyl chloride (“PVC”). In certain preferred examples, the polyolefins may include, for example, polyethylene, polypropylene, ethylene-butene copolymer, and any combination thereof, but preferably polyethylene. In certain examples, exemplary natural or synthetic rubbers may include, for example, latex, uncross-linked or cross-linked rubbers, crumb or ground rubber, and any combination thereof.Polyolefins

[0171] In certain examples, the microporous substrate layer is a polyolefin, specifically polyethylene. In one example, the polyethylene is high molecular weight polyethylene (“HMWPE”), (e.g., polyethylene having a molecular weight of at least 600,000). In other examples, the polyethylene is ultra-high molecular weight polyethylene (“UHMWPE”) (e.g., polyethylene having a molecular weight of at least 1 ,000,000, more than 4,000,000, or 5,000,000 to 8,000,000 as measured by viscometry and calculated by Margolie's equation), a standard load melt index of substantially zero (0) (measured as specified in ASTM D 1238 (Condition E) using a standard load of 2,160 g) and a viscosity number of not less than 600 ml / g, preferably not less than 1 ,000 ml / g, more preferably not less than 2,000 ml / g, and most preferably not less than 3,000 ml / g (determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130° C.).

[0172] The substrate 100 coated separator 724 disclosed herein may contain latex and / or rubber. As used herein, rubber shall describe, rubber, latex, natural rubber, synthetic rubber, cross-linked or uncross-linked rubbers, cured or uncured rubber, crumb or ground rubber, or mixtures thereof. Exemplary natural rubbers may include one or more blends of polyisoprenes, which are commercially available from a variety of suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubbers, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulphide rubber, chlorosulphonyl polyethylene, polynorbornene rubber, acrylate rubber, fluorine rubber and silicone rubber and copolymer rubbers, such as styrene / butadiene rubbers, acrylonitrile / butadiene rubbers, ethylene / propylene rubbers (“EPM” and “EPDM”) and ethylene / vinyl acetate rubbers. The rubber may be a cross-linked rubber or an uncross-linked rubber; in certain preferredexamples, the rubber is uncross-linked rubber. In certain examples, the rubber may be a blend of cross-linked and uncross-linked rubber.Substrate Plasticizer

[0173] In certain examples, exemplary processing plasticizers for the substrate 100 may include processing oil, petroleum oil, paraffin-based mineral oil, mineral oil, and any combination thereof. In the final substrate, oil content is preferably 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11 % or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less. The residual oil content of a wet process polyolefin substrate or membrane is typically greater than 0%.Substrate Fillers

[0174] In certain examples, exemplary fillers for the substrate 100 may include: dry finely divided silica; precipitated silica; amorphous silica; alumina; talc; fish meal, fish bone meal, and the like, and any combination thereof. In certain preferred examples, the filler is one or more silicas. Silica with relatively high levels of oil absorption and relatively high levels of affinity for the plasticizer (e.g., mineral oil) becomes desirably dispersible in the mixture of the polyolefin base material (e.g., polyethylene) and mineral oil when forming a lead acid battery coated separator 724 of the type shown herein. In some selected examples, the filler has an average particle size no greater than 25 pm, in some instances, no greater than 22 pm, 20 pm, 18 pm, 15 pm, or 10 pm. In some instances, the average particle size of silica filler particles is 15-25 pm. The particle size of the silica filler and / or the surface area of the silica filler contributes to the oil absorption. Silica particles in the final product or coated separator 724 may fall within the sizes described above. However, the initial silica used as raw material may come as one or more agglomerates and / or aggregates and may have sizes around 200 pm or more. In some examples, the final coated separator 724 sheet has a residual or final oil content in a range of about 0.5% to about 40%, in some examples, about 10% to about 30% residual processing oil, and in some instances, about 20 to about 30% residual processing oil or residual oil, per the weight of the coated separator 724 sheet product. Regarding pore size of the coated separator 724 microporous substrate (or membrane; hereinafter “microporous substrate” is used interchangeably with “membrane”), as measured by aCapillary Flow Porometer, the pore size may be submicron up to 100 pm, and in certain examples between about 0.1 pm to about 10 pm. Porosity of the coated separator 724 membrane described herein may be greater than 50% in certain examples. In some examples, the microporosity of the microporous substrate is between 0.3 - 1 urn as measured via Hg-porosimetry.

[0175] The fillers present in the substrate 100 may further reduce what is called the hydration sphere of the electrolyte ions, enhancing their transport across the membrane, thereby once again lowering the overall electrical resistance or ER of the battery, such as an enhanced flooded battery or system.

[0176] The filler or fillers may contain various species (e.g., polar species, such as metals) that facilitate the flow of electrolyte and ions across the coated separator 724. Such also leads to decreased overall electrical resistance as such a coated separator 724 is used in a flooded battery, such as an enhanced flooded battery.

[0177] In certain selected examples, the separator substrate or membrane may be prepared by combining, by weight, about 5-15% polymer, in some instances, about 10% polymer (e.g., polyethylene), about 10-75% filler (e.g., silica), in some instances, about 30% filler, and about 10-85% processing oil, in some instances, about 60% processing oil. In other examples, the filler content is reduced, and the oil content is increased, for instance, greater than about 61 %, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70% by weight. In one example, the filler: polymer ratio (by weight) is about (or may be between about these specific ranges) such as 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. In one example, the fillenpolymer ratio (by weight) is from about 1.5:1 to about 6:1 , in some instances, 2:1 to 6:1 , from about 2:1 to 5:1 , from about 2:1 to 4:1 , and in some instances, from about 2:1 to about 3:1 . The amounts of the filler, the oil, and polymer are all balanced for runnability, manufacturability and desirable separator properties, such as electrical resistance, ion conductivity, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, tortuosity, and the like.

[0178] In accordance with at least one example, the microporous substrate can include an IIHMWPE mixed with a processing oil and precipitated silica. In accordance with at least one example, the microporous substrate can include an UHMWPE mixed with a processing oil, additive and precipitated silica. The mixture may also include minoramounts of other additives or agents as is common in the separator arts (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like, and any combination thereof). In certain instances, the microporous polymer layer may be a homogeneous mixture of 8 to 100% by volume of polyolefin, 0 to 40% by volume of a plasticizer and 0 to 92% by volume of inert filler material. The preferred plasticizer is petroleum oil. Since the plasticizer is the component which is easiest to remove, by solvent extraction and drying, from the polymer-filler-plasticizer composition, it is useful in imparting porosity to the battery separator.

[0179] In certain examples, the microporous substrate disclosed herein may contain latex and / or rubber, which may be a natural rubber, synthetic rubber, or a mixture thereof. Natural rubbers may include one or more blends of polyisoprenes, which are commercially available from a variety of suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubbers, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulphide rubber, chlorosulphonyl polyethylene, polynorbornene rubber, acrylate rubber, fluorine rubber and silicone rubber and copolymer rubbers, such as styrene / butadiene rubbers, acrylonitrile / butadiene rubbers, ethylene / propylene rubbers (EPM and EPDM) and ethylene / vinyl acetate rubbers. The rubber may be a cross-linked rubber or an uncross-linked rubber; in certain preferred examples, the rubber is uncross-linked rubber. In certain examples, the rubber may be a blend of cross-linked and uncross-linked rubber. The rubber may be present in the coated separator 724 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 (the weight of the polyolefin separator sheet or layer containing rubber and / or latex). In certain examples, the rubber may be present in an amount from about 1-20%, 2-20%, 2.5-15%, 2.5-12.5%, 2.5-10%, or 5-10% by weight. The microporous substrate may even have a rubber and / or latex content as high as 50% by weight. The amounts of the rubber, filler, oil, and polymer are all balanced for runnability and desirable separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, tortuosity, and the like.

[0180] A microporous substrate made in accordance with the present disclosure, comprising polyethylene and filler (e.g., silica) typically has a residual oil content; in someexamples, such residual oil content is from about 0.5% up to about 40% of the total weight of the coated separator 724 membrane (in some instances, 5-40% of that total weight of the coated separator, about 10-40% of the total weight of the coated separator 724 membrane, and in some instances, about 20-40% of that total weight). In certain selected examples herein, some to all of the residual oil content in the coated separator 724 may be replaced by the addition of more of a performance enhancing additive, such as a surfactant, such as a surfactant with a hydrophilic-lipophilic balance (“HLB”) less than 6, or such as a nonionic surfactant. For example, a performance enhancing additive such as a surfactant, such as a nonionic surfactant, may comprise up to 0.5% all the way up to all of the amount of the residual oil content (e.g., all the way up to 20% or 30% or even 40%) of the total weight of the microporous substrate, thereby partially or completely replacing the residual oil in the coated separator 724 membrane.

[0181] In one example, the coated separator 724 microporous substrate has pores less than about 5 pm, or less than about 1 pm, while a mesoporous substrate or a macroporous substrate may have pores greater than about 1 pm. In some examples, an exemplary microporous substrate is a microporous substrate having pore diameters of about 0.1 pm and a porosity of about 60%.Coating Formulation

[0182] The microporous substrate 100 is coated with a coating on one or both sides of the substrate. Such a coating includes mixture comprising a polymeric binder and an inorganic filler or siliceous material. In one example, the coating formulation comprises a polymeric binder, an inorganic filler, and a remainder of aqueous media and processing aids. Aqueous media can contain alcohol, either purposefully added or as a solvent for the binder. The mixture of polymeric binder and inorganic filler or siliceous material can be in the form of an emulsion, slurry or other dispersion or suspension.

[0183] The polymeric binder is dispersed in an aqueous solution that may include one or more polymerizable monomers or oligomers or polymers, including, but not limited to, one or more of butyl acrylate, styrene, and butadiene acrylonitrile styrene, and an emulsifier, including, but not limited to, one or more of alkyl benzene sulfonate, PEG, PPG, alkyl sulfate, polyoxyethylene alkyl ether, and alkyl sulfonate. In some examples the polymer binder may include formaldehyde or other crosslinking agents, such ascarbodim ides, polycarbodimides, and peroxides. In some examples the polymer binder includes water-borne or water soluble, such as carbodimides or polycarbodimides crosslinking agents. In one example, the polymeric binder does not include formaldehyde.

[0184] In one example, the polymeric binder is an acrylate, a methacrylate, a styrene, a polyurethane, a polyurethane-urea, a cellulosic derivative, or blends or grafts thereof. In one example, the polymeric binder is a non-elastomeric polymer. In another example the polymeric binder is combination of an elastomeric polymer with a cellulosic derivative, for example, carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose. The carboxymethyl cellulose (CMC), may increase viscosity and / or act as a binding agent. In one example the coating formulation comprises a polymeric binder as a mixture of a non- elastomeric polymer or elastomeric polymer, siliceous material, and a cellulosic derivative in a weight ratio of from 1 :2:0.1 to 1 :10:0.5, respectively.

[0185] In some examples, the siliceous material is at least one of a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, a mixture of two or more thereof, or a combination thereof. In some examples, the siliceous material is chemically modified or the surface thereof is functionalized, for example, with thermal stabilizer, wherein the thermal stabilizer is selected from the group consisting of alumina, zirconia, graphene, carbon nanotubes, and mixtures thereof. In some examples, the inorganic filler or siliceous material is present at 1 to 20 or 2 to 10 weight percent relative to the weight percent of the polymeric binder.

[0186] In one aspect or example, a coated battery separator, coated on one or both sides, is described and comprises the following combinations of silica in the coating: fumed silica, hydrophobic silica, precipitated silica and montmorillonite. In one embodiment, the silica in the coating on a preferred separator may be 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 0% wt. % fumed silica. In another embodiment, the silica in the coating on a preferred separator may be 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 0% wt. % hydrophobic silica. In yet another embodiment, the silica in the coating on a preferred separator may be 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 0% wt. % precipitated silica. In still another embodiment, the silica in the coating on a preferred separator may be 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 0% wt.% montmorillonite. In still yet another embodiment,the silica in the coating on a preferred separator may be about 33% wt. % fumed silica, 33% wt. % precipitated silica and 33% wt. % hydrophobic silica, about 25% wt. % fumed silica, 50% wt. % precipitated silica and 25% wt. % hydrophobic silica, about 50% wt. % fumed silica, 25% wt. % precipitated silica and 25% wt. % hydrophobic silica, about 25% wt. % fumed silica, 25% wt. % precipitated silica and 50% wt. % hydrophobic silica. In still yet another embodiment, the silica in the coating on a preferred separator may be about 33% wt. % fumed silica, 33% wt. % precipitated silica and 33% wt. % montmorillonite, about 25% wt. % fumed silica, 50% wt. % precipitated silica and 25% wt. % montmorillonite, about 50% wt. % fumed silica, 25% wt. % precipitated silica and 25% wt. % montmorillonite, about 25% wt. % fumed silica, 25% wt. % precipitated silica and 50% wt. % montmorillonite, or other combinations thereof.

[0187] The processing aids of the coating formulation, in some examples, comprises one or more of emulsifiers, surfactants, anti-foaming agents, adhesion promoters, antioxidants, UV stabilizers, curing aids, and crosslinking agents.

[0188] The coating disclosed herein exhibits improved ion conductivity. The coating can optionally contain hybrid organic / inorganic networks or doping with alkali / alkaline earth metals. In some examples, the coating may include a metallic sulfate selected from the group sodium sulfate, zinc sulfate, aluminum sulfate, lithium sulfate, magnesium sulfate, and mixtures thereof. The coating may contain anionic or cationic surfactants. In some examples, the coating may include a mixture of formed silica and precipitated silica. In some examples, the coating may be formed of montmorillonite, with the silica therein forming the basis of the performance characteristics of the coating described herein.Manufacture

[0189] In some examples, an exemplary microporous substrate may be made by mixing the constituent parts in an extruder. For example, about 30% by weight silica with about 10% by weight UHMWPE, and about 60% processing oil may be mixed in an extruder. The exemplary microporous substrate may be made by passing the constituent parts through a heated extruder, passing the extrudate generated by the extruder through a die and into a nip formed by two heated presses or calender stack or rolls to form a continuous web. In one example, a substantial amount of the processing oil from the web is extracted by use of a solvent. The web may then be dried and slit into lanes ofpredetermined width, and then wound onto rolls. In one example, presses or calender rolls engraved with various groove patterns to impart ribs, grooves, textured areas, serrations, serrated ribs, battlement or battlemented ribs, broken ribs, angled ribs, linear ribs, or curved or sinusoidal ribs, embossments, dimples, and / or the like extending in to or from the microporous substrate or its backweb, or any combination thereof is envisioned.

[0190] In some examples, an exemplary microporous substrate may be made by mixing the constituent parts in an extruder. For example, about 5-15% by weight polymer (e.g., polyethylene), about 10-75% by weight filler (e.g., silica), about 1 -50% by weight rubber and / or latex, and about 10-85% processing oil may be mixed in an extruder. The exemplary microporous substrate may be made by passing the constituent parts through a heated extruder, passing the extrudate generated by the extruder through a die and into a nip formed by two heated presses or calender stack or rolls to form a continuous web. A substantial amount of the processing oil from the web may be extracted by use of a solvent. The web may then be dried and slit into lanes of predetermined width, and then wound onto rolls. Alternatively or additionally, the presses or calender rolls may be engraved with various groove patterns to impart (as described hereinabove) ribs, grooves, textured areas, serrations, serrated ribs, battlement or battlemented ribs, broken ribs, angled ribs, linear ribs, or curved or sinusoidal ribs, embossments, dimples, and / or the like extending in to or from the microporous substrate, or any combination thereof into the coated separator 724. The amounts of the filler, oil, and polymer are all balanced for runnability and desirable separator properties, such as ion conductance, electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, tortuosity, and the like.

[0191] In one example, the coating formulation is introduced to at least one surface of the microporous substrate, the coating comprising a mixture of a polymeric binder and a siliceous material, and remainder of aqueous media and processing aids. The coating formulation can be applied to either surface of the microporous substrate. In one example, at least a portion of the polymeric binder and / or siliceous material penetrates or is absorbed by the microporous substrate. The coating formulation can be introduced to the microporous substrate as a emulsion, suspension, dispersion, slurry using any knownconventional coating technique such as blade coating, spray coating, curtain coating, or dip coating.

[0192] After coating, the microporous substrate with the coating formulation applied thereto is dried. In one example, drying initiates crosslinking or curing of the coating. After drying, a porous layer and / or conformal film forms on the surface of the separator, which adheres very well to the microporous substrate and / or any surface structures in one example, the dried coating maintains sufficient ion conductivity and increases electrical resistance of the microporous substrate insignificantly, if at all.

[0193] For better wettability of the microporous substrate prior to coating, adhesion promoters, surface modification techniques, or surface priming can be performed such as flame treatment or plasma treatment.

[0194] Target thicknesses of the coating range from 25 nm to 250nm. In some examples, in regions of the microporous substrate containing no ribs or protrusions, or only mini ribs or protrusion, no coating is applied in these areas to ensure it does not interfere with mechanical / ultrasonic sealing during the encapsulation of electrodes in pouches.

[0195] The coating may also have indentations as a result of the application thereof, either by additional manufacturing steps for imprinting indentations (such as, but not limited to, embossing). Additionally, or alternatively, the indentations may be formed as an inherent result of the application of the coating along a ribbed surface of the membrane. The indentations, using any method of formation thereof, may take the shape of channels, bumps, ridges, waves, dimples, or the like.

[0196] In one example, after drying / curing and / or crosslinking of the coated microporous substrate, it is presented to embossing roles which impart structural features to one or both sides as previously disclosed.

[0197] In one example, the polymer binder and silica are dispersed in an aqueous media at a bindersiliceous material ratio of between 1 :2 and 1 :6 wt% ratio. In some examples, the bindersiliceous material ratio is 1 :4.6 wt% ratio. In some examples, the bindersiliceous material ratio is 1 :10 wt% ratio.

[0198] In examples where the coating contains carboxymethyl cellulose (CMC) along with binder and silica, the binder:silica:CMC ratio is between 1 :2:0.1 and 1 :4:0.3 wt% ratio. In some examples, the binder:silica:CMC ratio is 1 :1.46:0.2 wt% ratio.

[0199] In certain examples, and in addition or alternative to adding into the extruder, the additive or additives may, for example, be applied to the 724 microporous substrate prior to coating (e.g., after extracting a bulk of the processing oil, and after the introduction of the ribs, protrusions, dimples). According to certain preferred examples, the additive or a solution (e.g., an aqueous solution) of the additive is applied to one or more surfaces of the separator. This variant is suitable in particular for the application of non-thermostable additives and additives which are soluble in the solvent used for the extraction of processing oil. Particularly suitable as solvents for the additives according to the disclosure are low-molecular-weight alcohols, such as methanol and ethanol, as well as mixtures of these alcohols with water. The application can take place on the side facing the negative electrode, the side facing the positive electrode, or on both sides of the coated separator 724. The application may also take place during the extraction of the pore forming agent (e.g., the processing oil) while in a solvent bath. In certain select examples, some portion of a performance enhancing additive, such as a surfactant coating or a performance enhancing additive added to the extruder before the coated separator 724 is made (or both) may combine with the antimony in the battery system and may inactivate it and / or form a compound with it and / or cause it to drop down into the mud rest of the battery and / or prevent it from depositing onto the negative electrode. The surfactant or additive may also be added to the electrolyte, to the glass mat, to the battery case, pasting paper, pasting mat, and / or the like.

[0200] In certain examples, the additive (e.g., a non-ionic surfactant, an anionic surfactant, or mixtures thereof) may be present at a density or add-on level of at least 0.5 g / m2, 1.0 g / m2, 1.5 g / m2, 2.0 g / m2, 2.5 g / m2, 3.0 g / m2, 3.5 g / m2, 4.0 g / m2, 4.5 g / m2, 5.0 g / m2, 5.5 g / m2, 6.0 g / m2, 6.5 g / m2, 7.0 g / m2, 7.5 g / m2, 8.0 g / m2, 8.5 g / m2, 9.0 g / m2, 9.5 g / m2 or 10.0 g / m2 or even up to about 25.0 g / m2. The additive may be present on the coated separator 724 at a density or add-on level between 0.5-15 g / m2, 0.5-10 g / m2, 1.0-10.0 g / m2, 1.5-10.0 g / m2, 2.0-10.0 g / m2, 2.5-10.0 g / m2, 3.0-10.0 g / m2, 3.5-10.0 g / m2, 4.0-10.0 g / m2, 4.5-10.0 g / m2, 5.0-10.0 g / m2, 5.5-10.0 g / m2, 6.0-10.0 g / m2, 6.5-10.0 g / m2, 7.0-10.0 g / m2, 7.5-10.0 g / m2, 4.5-7.5 g / m2, 5.0-10.5 g / m2, 5.0-11.0 g / m2, 5.0-12.0 g / m2, 5.0-15.0 g / m2, 5.0-16.0 g / m2, 5.0-17.0 g / m2, 5.0-18.0 g / m2, 5.0-19.0 g / m2, 5.0-20.0 g / m2, 5.0-21 .0 g / m2, 5.0-22.0 g / m2, 5.0-23.0 g / m2, 5.0-24.0 g / m2, or 5.0- 25.0 g / m2.

[0201] The application may also take place by dipping the battery separator in the additive or a solution of the additive (solvent bath addition) and removing the solvent if necessary (e.g., by drying). In this way the application of the additive may be combined, for example, with the extraction often applied during membrane production. Other preferred methods are to spray the surface with additive, dip coat, roller coat, or curtain coat the one or more additives on the surface of coated separator 724.

[0202] In certain examples described herein, a reduced amount of ionic, cationic, anionic, or non-ionic surfactant is added to the coated separator 724. In such instances, a desirable feature may include lowered total organic carbons and / or lowered volatile organic compounds (because of the lower amount of surfactant) may produce a desirable coated separator 724 according to such example.Coated Separator Combined with a Fibrous Mat

[0203] In contrast to the freely-fluid electrolyte in flooded lead acid batteries, in VRLA batteries the electrolyte is absorbed on a fiber or fibrous material, such as a glass fiber mat, a polymeric fiber mat, a gelled electrolyte, and so forth. In certain examples, exemplary coated separators according to the present disclosure may be combined with another layer (laminated or otherwise), such as a fibrous layer or fibrous mat having enhanced wicking properties and / or enhanced wetting or holding of electrolyte properties. The fibrous mat may be woven, nonwoven, fleeces, mesh, net, single layered, multilayered (where each layer may have the same, similar or different characteristics than the other layers), composed of glass fibers, or synthetic fibers, fleeces or fabrics made from synthetic fibers or mixtures with glass and synthetic fibers or paper, or any combination thereof.

[0204] In certain examples, the fibrous mat (laminated or otherwise) may be used as a carrier for additional materials. The additional material may include, for example, rubber and / or latex, optionally silica, water, and / or one or more performance enhancing additive, such as various additives described herein, or any combination thereof. By way ofexample, the additional material may be delivered in the form of a slurry that may then be coated onto one or more surfaces of the fibrous mat to form a film, or soaked and impregnated into the fibrous mat.

[0205] When the fibrous layer is present, it is preferred that the microporous substrate has a larger surface area than the fibrous layers. Thus, when combining the microporous substrate and the fibrous layers, the fibrous layers do not completely cover the microporous layer. It is preferred that at least two opposing edge regions of the membrane layer remain uncovered to provide edges for heat sealing which facilitates the optional formation of pockets or envelopes and / or the like. Such a fibrous mat may have a thickness that is at least 100 pm, in some examples, at least about 200 pm, at least about 250 pm, at least about 300 pm, at least about 400 pm, at least about 500 pm, at least about 600 pm, at least about 700 pm, at least about 800 pm, at least about 900 pm, at least about 1 mm, at least about 2 mm, and so forth. The subsequent laminated coated separator may be cut into pieces. In certain examples, the fibrous mat is laminated to a ribbed surface of the microporous substrate microporous substrate. In certain examples, handling and / or assembly advantages are provided to the battery maker with the improved separator described herein, as it may be supplied in roll form and / or cut piece form. And as mentioned previously, the improved separator may be a standalone separator sheet or layer without the addition of one or more fibrous mats or the like.

[0206] If the fibrous mat is laminated to the microporous substrate, they may be bonded together by adhesive, heat, ultrasonic welding, compression, and / or the like, or any combination thereof.

[0207] Referring now to FIG. 3, an exemplary microporous substrate separator 300 is provided with a backweb 302 with positive ribs 304 extending therefrom and substantially aligned in a machine direction (“MD”) of the separator. The coated separator 724 is further provided with negative ribs 310 substantially aligned in a machine direction of the coated separator 724 and substantially parallel to the positive ribs 304. The negative ribs 310 are intended to contact a negative electrode in an exemplary battery. While the negative ribs 310 in this illustrated example are substantially aligned in a machine direction of the coated separator 724, they may alternatively be substantially aligned in the crossmachine direction, typically known as negative cross-ribs.

[0208] With continued reference to FIG. 3, select examples of the coated separator 724 are provided with an array of positive ribs 304. The positive ribs 304 are provided with a base portion 306 that may extend the length of the coated separator 724 in the machine direction. Spaced teeth, discontinuous peaks, or other protrusions 308 may then extend from the surface of the base portion 306, such that the teeth 308 are raised above the underlying surface of the microporous substrate backweb 302. Furthermore, the base portion 306 may be wider than the teeth 308 themselves. The positive ribs 304 run substantially parallel to one another at. Exemplary rib teeth 308 of adjacent ribs 304 may be substantially in line with one another. However as pictured in FIG. 3, exemplary teeth 308 may be offset from one another from one rib 304 to an adjacent rib 304, either entirely or partially out of phase from an adjacent rib. As shown, the teeth 308 are entirely out of phase from one rib 304 to an adjacent rib.

[0209] As shown in FIG. 3, negative ribs are depicted as being substantially parallel to the machine direction of the coated separator 724. However, they may alternatively be substantially parallel to a cross machine direction. The depicted exemplary negative ribs are shown as being solid and substantially straight. However, they may alternatively be toothed in a generally similar manner as the positive ribs shown in FIG. 3.

[0210] It should be noted that the positive ribs may alternatively be placed in an exemplary battery such that they contact the negative electrode. Likewise, the negative ribs may alternatively be placed in an exemplary battery such that they contact the positive electrode.

[0211] In one example, the ribs on the first side (e.g., positive ribs) and the second side (e.g., negative ribs) may be the same. In another example, the ribs on the first side and the second side may be different. The ribs may be continuous on both sides, continuous on one side, but not on the other, discontinuous on both sides, or discontinuous on one side, but not on the other. In one example, the ribs on the first side and the second side are the same height. In another example, the ribs on the first side and the second side are different heights. Further, rib heights on a given side are the same or different. In another example, the rib spacing on the first side may be the same as the spacing on the second side. In another example, the rib spacing on the first side may be different thanthe spacing on the second side. Rib spacing may also be variable on the same side. A combination of different rib heights and spacings may also be combined on one side.

[0212] Rib spacing is not so limited, but is preferably from 0.25 mm to 12 mm, from 0.5mm to 12 mm, from 1 mm to 12 mm, from 2 to 12 mm, from 3 to 12 mm, from 4 to 12 mm, from 5 mm to 12 mm, from 6 mm to 12 mm, from 7 mm to 12 mm, from 8 mm to 12 mm, from 9 mm to 12 mm, from 10 mm to 12 mm, or from 11 mm to 12 mm.

[0213] In examples including discontinuous ribs, the ribs may be angled or not angled. For example, for an angled rib, the angle of the rib may be 1 degree or more or less than 180 degrees, or the angle of the rib may be from 181 degrees or greater to less than 360 degrees.

[0214] FIG. 4 includes four views of the profile of a serrated coated separator 724 used in accordance with various examples described herein.Coated Separator Combined with a Gauntlet or Coated GauntletTubular batteries contain a gauntlet, which is typically a woven or nonwoven component. Gauntlets ensure good contact between the positive active material (PAM) and the positive plate spines, better containing any shedding of this material during loading / discharging phases, and allowing for easier production of these plates at the same time. Thus, in a tubular battery, the gauntlet is typically in intimate contact with at least the positive active material (PAM) of the positive electrode. Therefore, in these batteries, it would be beneficial to coat the gauntlet instead of or in addition to coating the separator. The silica coating on the gauntlet will absorb acid substantially uniformly and hold the acid up against the positive active material (PAM) of the positive electrode, preventing acid stratification. Due to the location of the gauntlet in a tubular battery, applying a silica coating to the gauntlet allows for the maximum capture of electrolyte to prevent stratification. Silica coating on both the gauntlet and the separator in a tubular battery may be preferred. Oxidation of the separator would also be improved with the silica coating.Manufacturing of Batteries with Presently Disclosed Coated Separators

[0215] The method of manufacturing batteries may begin with the insertion of the coated separator 724 of the present disclosure between the positive and negative electrodes of the lead acid battery. Next, the lead acid battery is filled with electrolyte, astep that traditionally requires the use of a vacuum to ensure optimal electrolyte penetration and distribution. However, in contrast to conventional methods, the present disclosure eliminates the need for a vacuum during the filling process, significantly reducing production time and resource utilization.

[0216] Upon completion of the filling process, the lead acid battery is sealed to prevent leakage and ensure the integrity of the electrolyte within the battery casing. The filling process may be completed in four minutes or less and three minutes or less.

[0217] Referring now to FIGS. 5 and 6, an electrode surface is shown having an unsupported surface area or portion, and a discontinuous supported surface area or portion (cross-hatched portions). A more detailed portion of FIG. 5 is depicted in FIG. 6. Point A is shown as a point on the midpoint of an edge of a supported portion, and point B is shown as a point on an end of a supported section. Their respective encompassing circles define the unsupported distance from one supported portion to an adjacent supported portion. It is appreciated that FIGS. 5 and 6 are not drawn to scale.

[0218] With a standard electrode width of 160 cm, there can typically be 11 to 18 ribs spaced uniformly along the cross-machine direction of the coated separator 724, this yields a typical unsupported distance between adjacent supported portions is approximately 13 mm to 8 mm, respectively. By making the ribs narrow and segmenting them while keeping the same rib mass as a typical separator with solid ribs, the number of ribs on a 160 cm wide electrode could be increased to approximately 20 to about 40 or more ribs. This allows the unsupported distance between ribs to be approximately 3 mm to approximately 4 mm or less. For example, the unsupported distance may be as close as approximately 1.5 mm depending upon the pitch of the serrations or teeth and the spacing of the ribs.

[0219] FIG. 8 illustrates microscope images of a coated separator 724, in accordance with examples of the separator of the disclosure. FIG. 8 illustrates a coated layer adjacent the membrane 705. The coating when applied to a separator swells 10%, 50%, up to about 75% by volume upon contact with acid of a specific gravity above 1.1. In a lead acid battery, flooded battery, or valve-regulated battery (including either absorptive glass mat (AGM) or gelled) that includes the coated separator 724 described herein and >1.20Sp. Gr. sulfuric acid, the silica in the coating absorbs the acid and swells by 30% to 70%, subsequently decreasing a gap between the coated separator 724 and an electrode.

[0220] FIG. 9 illustrates side views of a coated separator 724 between electrodes, in accordance with examples of the separator of the disclosure. Coated separator 724 includes a coating 712 between the positive electrode 702 and the negative electrode 704. In the present example, the coated separator 724 includes ridges adjacent the positive electrode 702, with the coating applied to the side of the coated separator 724 adjacent the positive electrode 702. However, it shall be appreciated that the example illustrated in FIG. 9 is merely for illustrative purposes only, and that the mechanism of action of the coated separator 724 and resulting effects are found in various other example configurations, as will be discussed in greater detail herein.

[0221] Upon coming into contact with sulfuric acid, the portions of the acid that come into contact with the coating 712 become gelled and have an expanded volume, allowing free-flowing sulfuric acid 730 to permeate between ridges of the coated separator 724.

[0222] FIG. 10 illustrates side views of a coated separator 724 between electrodes, in accordance with examples of the separator of the disclosure.

[0223] FIG. 11 illustrates side views of a control cell and cell containing separators between electrodes, in accordance with examples of the separator of the disclosure. The control battery cell depicted in FIG. 11 illustrates a traditional AGM battery design, where the uncoated separator 720 (e.g., the control separator) assumes a continuous configuration, encircling both the positive and negative electrodes. In contrast, in one example of the coated separator 724 shown in FIG. 5, the coated separator 724 includes a discontinuous layout wrapped exclusively around the positive electrode(s). In this example, the "X" side of the membrane exhibits ridges oriented towards the positive electrode, perpendicular to the battery cell's top and bottom. Meanwhile, the ridges on the "U" side align parallel to the cell's top and bottom surfaces.

[0224] FIGS. 12 and 13 illustrate side views of separators between electrodes, in accordance with examples of the separator of the disclosure. As used herein, an “N- wrapped” separator may refer to a separator wrapped around the negative electrode 704 of a cell, while a “P-wrapped” separator may refer to a separator wrapped around the positive electrode 702 of a cell. Additionally, nomenclature of a separator which ends ina “(+)”, such as “EFS-19X(+)”, refers to the position of the coating 712, such that the coating 712 is proximate the positive electrode. Alternatively, the nomenclature of a separator which ends in asuch as “EFS-19X(-)”, refers to the position of the coating 712, such that the coating 712 is proximate the negative electrode.

[0225] Accordingly, FIG. 12 illustrates examples of a control, an N-wrapped coated separator 724 having the coating 712 proximate the positive electrode, and an N-wrapped coated separator 724 having the coating 712 proximate the negative electrode. FIG. 13 illustrates examples of a control, an N-wrapped coated separator 724 having the coating 712 proximate the positive electrode, and P-wrapped separators 724 having the coating 712 proximate the positive electrode. Of course, another example not shown graphically in FIGS. 12 or 13 includes a P-wrapped coated separator 724 having the coating 712 proximate the negative electrodes. While the illustrations of FIGS. 12 and 13 generally depict battery cells having two positive electrodes 702 and one negative electrode 704, it shall be appreciated that the electrode configuration of the cell is presented in truncated form merely for illustrative purposes. Indeed, one example of a cell may include 1 positive electrode 702 and 1 negative electrode 704. Another example of a cell may include 2 positive electrodes 702 and 1 negative electrode 704 in an alternating configuration. Another example of a cell may include 1 positive electrode 702 and 2 negative electrodes 704 in an alternating configuration. Another example of a cell may include 2 positive electrodes 702 and 3 negative electrode 704 in an alternating configuration. Yet another example of a cell may include 3 positive electrodes 702 and 3 negative electrode 704 in an alternating configuration, and so forth. Indeed, there may be as many or few positive electrodes 702 and negative electrodes 704 as necessary for any given required cell.

[0226] As described above, the battery separators described herein are used in either flooded lead acid (“FLA”) batteries or in valve-regulated lead acid (“VRLA”) batteries, including gel batteries and absorbent glass matt (“AGM”) batteries.

[0227] In some examples, the battery separators described herein are used in flooded lead acid batteries where lower acid stratification is desired. This may include enhanced flooded batteries (EFBs), start-light-ignite (SLI) batteries, tubular batteries, flow batteries, storage batteries, accumulators, or the like. The battery is a main battery or an auxiliary battery. It is believed that the improved battery separators described herein may allowfor the use of flooded lead acid batteries as auxiliary batteries, which is currently difficult. An auxiliary battery, as understood by one skilled in the art, an auxiliary battery is not primarily responsible for starting the engine of a vehicle, though it may be a backup.

[0228] In other examples, the battery separators described herein are used in a valve- regulated lead acid (VRLA) battery, particularly a VRLA battery for use as an auxiliary battery in a vehicle or a tubular (gel) VRLA battery. The coated separator 724 may also be used in a VRLA battery that is a main battery in a vehicle.

[0229] Vehicles as described herein may include trucks, cars with internal combustion engines (ICEs), hybrid ICE’s, electric cars, carts, golf carts, bicycles, motorcycles, rickshaws, fork lifts, RVs, trucks, or the like. Other devices may include ESS, BPS, UPS, grid storage, renewable energy storage, etc.

[0230] Batteries described herein may also be used in devices such as solar power systems, telecommunications systems, signaling systems (for railway stations, airports, and seaports), monitoring and control systems, Uninterruptible Power Sources (UPSs), and renewable energy systems. Tubular batteries may be particularly useful for these types of applications where space and weight constraints are less of an issue.Separator Rib Profiles

[0231] To prepare the Examples, silica-filled polyethylene uncoated separators 720 with 5-20% processing oil were obtained. The uncoated separators 720 had different rib profiles:

[0232] Profile 1 (the “19X” profile) is where on one side of the separator the rib profile is a discontinuous vertical rib, where adjacent rib pitch is approximately 4.5 mm. On the other side, the rib profile is a continuous rib that runs perpendicular to the ribs on the other side (i.e. , a cross-rib), where adjacent rib pitch is approximately 3.6 mm. See FIG. 3.

[0233] Profile 2 (the “U” profile, or “UX”) is where on one side of the separator the rib profile is a continuous vertical rib, where adjacent rib pitch is approximately 0.67 mm. See FIG. 4.Testing and ResultsTest 1Example 1 (“EFS-19X(+)”)

[0234] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The positive electrode plates were wrapped with the coated separator 724 so that the cross-rib faced the positive electrode plate and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profile of the coated separator 724 facing the positive plate.Example 2 (“EFS-19X(-)”):

[0235] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The positive electrode plates were wrapped with the coated separator 724 so that the cross-rib faced the positive plate and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profile of the coated separator 724 facing the negative plate. Example 3 (control) (“EFS-19X”):

[0236] One or more uncoated separators 720 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The positive electrode plates were wrapped with the uncoated separator 720 so that the cross-rib faced the positive plate and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to a profile of the uncoated separator 720.

[0237] FIG. 14 illustrates a graph of data obtained using a hydrometer which plots change in specific gravity to number of cycles, in accordance with examples of the coated separator 724 of the disclosure. Similarly, FIG. 15 illustrates a graph of data obtained using a voltmeter which plots average EoD voltage to number of cycles, in accordance with the examples of the coated separator 724 of FIG. 14.

[0238] To determine one ideal position of the coating 712, such as the coating 712 being proximate the positive electrode or proximate the negative electrode, the performance of various examples of the present disclosure was evaluated as it relates to the change in specific gravity and end of discharge voltage.

[0239] Ideally, the change in specific gravity of the sulfuric acid in a battery cell over an extended number of cycles of the battery cell is minimized to indicate reduced stratification. The testing reflected in FIG. 14 was performed exclusively with P-wrapped samples with 2 negative electrodes and 1 positive electrode therebetween, and a compression of approximately 20kPa. First, the specific gravity of the sulfuric acid in a control sample of an AGM separator was sampled at a predetermined interval between 0 and over 500 cycles and plotted on the graph of FIG. 14. The specific gravity of the sulfuric acid in a control sample including a uncoated separator 720 was sampled at a predetermined number of intervals between 0 and over 600 cycles and plotted on the graph of FIG. 14. Next, the specific gravity of the sulfuric acid in a cell having a coated separator 724 coated on the side proximate the negative electrode was sampled at a predetermined interval between 0 and 600 cycles and plotted on the graph of FIG. 14. Finally, the specific gravity of the sulfuric acid in a cell having a coated separator 724 coated on the side proximate the positive electrode was sampled at a predetermined interval between 0 and 600 cycles and plotted on the graph of FIG. 14.

[0240] While the AGM separator control sample resulted in the least amount of change in specific gravity, it is clear from FIG. 14 that a coated separator 724 coated on the side proximate the positive electrode led to less change in specific gravity through the tested number of cycles than both the uncoated sample and the sample coated on the side proximate the negative electrode. Thus, the presently disclosed coated separator provides for reduced acid stratification in lead-acid batteries.

[0241] Ideally, the end of discharge voltage of a battery cell remains constant over an extended number of cycles of the battery cell to ensure consistent performance and reliability of the battery, prolong its lifespan, and minimize the risk of damage to connected devices or systems relying on the battery's power supply. The testing reflected in FIG. 15 used the same battery cells as those from FIG. 14, such that end of discharge evaluation was performed exclusively with P-wrapped samples with 2 negative electrodes and 1 positive electrode therebetween, and a compression of approximately 20kPa. First, the average end of discharge voltage of a control sample of an AGM separator was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 15. The average end of discharge voltage of a control sample including auncoated separator 720 was sampled at a predetermined number of intervals between 0 and over 1000 cycles and plotted on the graph of FIG. 15. Next, the average end of discharge voltage of a cell having a coated separator 724 coated on the side proximate the negative electrode was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 15. Finally, the average end of discharge voltage of a cell having a coated separator 724 coated on the side proximate the positive electrode was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 15.

[0242] The data on the graph of FIG. 15 was then evaluated. While the AGM separator control sample resulted in the least amount of change / reduction in average end of discharge voltage over the cycles, it is clear that a coated separator 724 coated on the side proximate the positive electrode led to less change / reduction in average end of discharge voltage through the tested number of cycles than both the uncoated sample and the sample coated on the side proximate the negative electrode.

[0243] FIG. 16 illustrates a graph of data obtained using a voltmeter which plots terminal discharge voltage to number of cycles, in accordance with examples of the separator of the disclosure. The graph of FIG. 16 provides insight into the stratification over time, via changes in terminal discharge voltage over time. Minimal decrease to terminal discharge voltage through 1000 cycles indicates a minimal amount of stratification, which ultimately leads to consistent communication of a battery management system.

[0244] A total of six samples of P-wrapped separators 700, six samples of N-wrapped separators 700, and three samples of uncoated separator 720 separators were subjected to up to 1000 cycles (if there was any remaining terminal discharge voltage at that point), with terminal discharge voltage captured at a predetermined interval. As evident by FIG. 16, the P-wrapped coated separators provided much less loss of terminal discharge voltage throughout the 1000 cycles than that of the N-wrapped separators. Moreover, both the P-wrapped and N-wrapped coated separators greatly outperformed the uncoated separator 720 separator control, all of which failed prior to reaching 1000 cycles.

[0245] FIG. 17 illustrates a graph of data obtained using a hydrometer, which plots the difference in specific gravity between top and bottom, in accordance with examples of thecoated separator of the disclosure. A control of an uncoated separator 720 at 174cy exposed to a 2v cell PSoC cycle life test led to a difference in specific gravity between the top of the cell and the bottom of the cell of 0.116. N-wrapped 110 micron thickness (umt) and 240umt samples as well as a P-wrapped 120umt coated separator 724 sample under the same conditions showed some reduction in the difference between specific gravity between the top and bottom of the cell. However, the P-wrapped 270umt coated separator 724 at 174cy exposed to the 2v cell PSoC cycle life test led to a difference in specific gravity between the top of the cell and the bottom of the cell of 0.030, showing a significant improvement in acid stratification compared to the uncoated separator 720.

[0246] FIGS. 18 and 19 illustrate images of a control uncoated separator 720 and a coated separator 724 after a cycle life test. The specific test was the Volkswagen (VW) 17.5% PSoC cycle life test an industry standard test that measures a battery's ability to operate in a partial charge state to evaluate a battery's mid-depth cycling and recharge capability.Example 4 (control):

[0247] One or more uncoated separators 720 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the uncoated separator 720 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to the uncoated separator 720.Example 5:

[0248] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the positive plates.Example 6:

[0249] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The positive electrode plates were wrapped with the coated separator 724 so that the cross-rib faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the positive plates.

[0250] The uncoated separator 720 in FIG. 18 shows significant stratification, as made evident by the soft deposits at the upper portions of the positive side of the control separator, and sulfated deposits at the bottom portions of the positive side of the control separator. Further, the negative side (not pictured in FIG. 18) of the uncoated separator 720 contained soft deposits throughout.

[0251] In contrast, the coated separator 724 in a P-wrapped configuration shown in FIG. 19 showed only slight surface sulfation and no evident stratification after the same cycle life test. Further, the positive side of the coated separator 724 only contained slightly softened deposits throughout. N-wrapped configurations of the coated separator 724 performed similarly. Clearly, as shown in FIGS. 18 and 19, the use of a coating on the separator greatly improved its resistance to stratification and sulfation.Test 2Example 7 (“[EFS-19X(-)J”)

[0252] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. A coating was applied to the profiles of the coated separator 724 facing the positive plates.Example 8 (“[EFS-19X(+)]”):

[0253] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween wereprepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the negative plate.Example 9 (“EFS-19X(-)”):

[0254] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the negative plate.Example 10 (!EFS-19X(+)”):

[0255] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the positive plates.Example 11 (control - “EFS-19X”):

[0256] One or more uncoated separators 720 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the uncoated separator 720 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to either profile of the uncoated separator 720.Example 12 (control - “[EFS-19X]”):

[0257] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween wasprepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-rib faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the positive plates.

[0258] FIG. 20 illustrates a graph of data obtained using a voltmeter which plots average voltage to number of cycles, in accordance with examples of the disclosed separator. FIG. 21 illustrates side views of coated separators 724 and uncoated separators 720 between electrodes, in accordance with examples of the separator of the disclosure, and more specifically the examples used for the test which resulted in the graph of FIG. 20. The average voltages of six example coated separators 724 and uncoated separators 720 were plotted on the graph during a 2\Z 17.5% Continuous PSoC test up to 2500 cycles, restarting the test every 1000 hours. As shown in FIG. 20, the reverse orientation of the coated separators 724 achieved higher average voltages during the duration of the test than other examples, without exhibiting drop-offs in average voltage. All of the coated separator examples 724 maintained higher average voltages for significantly higher number of cycles as compared to uncoated separators 720, a clear indication of improved performance.Test 3Example 13 (AGM):

[0259] Example 13 is one or more AGM separators were provided and otherwise unmanipulated (controls).Example 14 (“U250X” uncoated - control):

[0260] One or more uncoated separators 720 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the uncoated separator 720 so that the cross-ribs faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to the profiles of the uncoated separator 720.Example 15 (“U250X- single side coated”):

[0261] One or more coated separators 724 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. A coating was applied to the profiles of the coated separator 724 facing the negative plate. Example 16 (“U250X- double side coated”):

[0262] One or more coated separators 724 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to both profiles of the coated separator 724 facing both the negative and the positive plates.

[0263] FIG. 22 illustrates a graph of data obtained using a voltmeter which plots average discharge voltage to number of cycles, in accordance with examples of the separator of the disclosure. To compare the difference in discharge voltage at 468 cycles, several examples of coated separators 724, including double-sided and single-sided coated separators 724, and a control sample of an AGM separator, were each subjected to 17.5% DOD PSOC cycling performance testing. Notably, the AGM separator was compressed to 30%, while the coated separators 724 were compressed to 5%. Despite this difference in amount of compression, the average discharge voltages of the coated separators 724, regardless of the placement of coating, were substantially similar to that of the AGM separator. This similarly shows that an end of discharge voltage similar to the AGM separator may be achieved with much less compression required, leading to improved manufacturing efficiencies.

[0264] FIG. 23 illustrates a graph of data which plots oxidation lifetime, in accordance with examples of the disclosed separator. It is known that a positive electrode of a battery cell may react with various separators in a manner such as to puncture, perforate, corrode, or otherwise degrade the separator. Indeed, FIG. 24A illustrates an image of an uncoated control sample separator 720 after an oxidation lifetime test. FIG. 24Billustrates an image of a separator 724 after the oxidation lifetime test, in accordance with examples of the separator of the disclosure.

[0265] As shown clearly in FIG. 24A, a hole 726 may appear through the uncoated separator 720 as a result of oxidation, and lead to poor battery cell performance and failure.

[0266] The lifetime oxidation test led to the control sample separator 720 obtaining the hole 726 after 83.9 hours. The same oxidation lifetime test performed on a coated separator 724 led to the coated separator 724 remaining intact and free from significant damage until 158.5 hours, at which point a hole 726 was formed. The resulting oxidation lifetime, expressed in number of hours, is shown graphically in FIG. 23.

[0267] In contrast to the control separator 720 (e.g., uncoated), there is a clear improvement in the oxidation lifespan of separators of approximately 88 percent by applying the presently disclosed coating 712.

[0268] FIGS. 25-27 illustrate data of various tests performed on single-sided coated, double-sided coated, and uncoated separators 720 to compare performance of said separators to AGM separators. FIG. 25 illustrates a graph of data obtained using a voltmeter which plots discharge voltage to step time, in accordance with examples of the separator of the disclosure. FIG. 26 illustrates a graph of data obtained using a voltmeter which plots average discharge capacity to number of cycles, in accordance with examples of the separator of the disclosure. FIG. 27 illustrates a graph of data obtained using a voltmeter which plots discharge capacity to number of cycles, in accordance with examples of the separator of the disclosure.

[0269] The separators with a PE substrate, such as the single-sided coated, doublesided coated separators 724, and uncoated separators 720 were brought to 5% compression, while the AGM separator was brought to a 30% compression.

[0270] As a result of testing, it was concluded that double-sided coated separators 724 improve capacity of battery cells over their AGM counterparts by about 15%. As shown in FIG. 25, double-sided coated separators 724 experienced the longest step time duration prior to discharge voltage being significantly reduced, thus providing a longer battery duration. Both uncoated and single-sided coated separators 724 similarly outperformed AGM separators. FIG. 26 shows that double-sided coated separators 724retain discharge capacity for a larger number of cycles than compared to both singlesided coated separators 724 and uncoated separators 720. All three outperformed the AGM separator in the same test. FIG. 27 illustrates that double-sided coated separators 724 retain discharge capacity for a larger number of cycles than compared to both singlesided coated separators 724 and uncoated separators 720. All three outperformed the AGM separator in the same test. FIG. 27 illustrates that U100um and D100um, as well as uncoated separators 720, retain discharge capacity for a larger number of cycles than compared to the AGM separator undergoing the same test.

[0271] FIGS. 28 and 29 illustrate time-sequenced images of the filling of a battery having a coated separator 724, and a battery having an AGM, in accordance with examples of the separator of the disclosure. The sequence of five images depicted in FIG. 28 depict the process of sulfuric acid dispersion onto a coated separator 724 without vacuum assistance. Starting with the initial state of the coated separator 724 before acid introduction, subsequent images portray the progressive dispersion and absorption of sulfuric acid at intervals of 5, 30, 60, and 140 seconds. Notably, the final image depicts complete dispersion of the sulfuric acid achieved within a span of 140 seconds. In contrast, FIG. 29 illustrates the dispersion of sulfuric acid within an AGM under vacuum pressure, and as a result providing a comparison to the non-vacuum coated separator 724 showcased in FIG. 28. Despite vacuum application, the AGM shows limited acid dispersion at 60 and 120 seconds, with full dispersion achieved only after an extended duration of 1200 seconds. This juxtaposition underscores the improvements of the nonvacuum coated separator 724, which increases efficiency over AGM separators requiring vacuum-assistance.Test 4Example 17 (AGM):

[0272] Example 17 is one or more AGM separators were provided and otherwise unmanipulated.Example 18 (control - “EFS-19X” “uncoated”):

[0273] One or more uncoated separators 720 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the uncoated separator 720so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to either profile of the uncoated separator 720.Example 19 (lEFS-19X(+)”):

[0274] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to the profiles of the coated separator 724 facing the positive plates.Example 20 (l‘[EFS-19X(-)]”)

[0275] One or more coated separators 724 having profile 1 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. A coating was applied to the profiles of the coated separator 724 facing the positive plates.

[0276] FIG. 30 illustrates a graph of data obtained using a voltmeter which plots average end of discharge voltage to number of cycles, in accordance with examples of the separator of the disclosure. FIG. 31 illustrates a graph of data obtained using a hydrometer which plots the difference in specific gravity between top and bottom to number of cycles, in accordance with examples of FIG. 30. Samples of separators were produced, each of which contained two positive electrodes and one negative electrode. P-wrapped separators having a coating adjacent the positive electrode were produced, as well as uncoated separators 720 and AGM separators for comparison.

[0277] Subjecting each separator to a VW 17.5% DOD PSOC cycle life test, the reduced stratification in the coated separators 724 led to a more stable voltage over a longer life compared to uncoated separators 720, as shown in FIG. 30. The AGM separator and the coated separator 724 exhibited similar lifespans, with the AGM havinga slightly higher discharge voltage. Turning to FIG. 31 , the uncoated separator 720 experienced a higher difference in specific gravity (between the top of the battery cell and the bottom of the battery cell) throughout the 2v cell PSoC cycle life testing, attributed to stratification. On the other hand, the coated separator 724 and AGM separator showed minimal specific gravity gradients between the top and bottom of the cell battery.

[0278] As a result, a battery containing a coated separator 724 will exhibit a stable voltage consistent with typical AGM VRLA, which corresponds to a A Specific Gravity (SpG) between a bottom and a top of an acid in the battery is less than 0.06 at 100 cycles, or less than 0.06 at 500 cycles. Further, a battery containing a coated separator 724 will exhibit a cycle life consistent with a typical Gel VRLA battery, which is between 500 and 1500 cycles at 50%depth of discharge (DOD). Further still, a battery containing a coated separator 724 will exhibit a cycle life consistent with a typical Gel VRLA battery, which is between 500 and 1500 cycles at 80% depth of discharge (DOD).

[0279] FIG. 32 illustrates a graph of data obtained using a hydrometer which plots change in specific gravity to number of cycles, in accordance with examples of the separator of the disclosure. Similarly, FIG. 33 illustrates a graph of data obtained using a voltmeter which plots average EoD voltage to number of cycles, in accordance with the examples of the separator of FIG. 32.

[0280] To determine one ideal position of the coating 712, such as the coating 712 being proximate the positive electrode or proximate the negative electrode, the performance of various examples of the present disclosure was evaluated as it relates to the change in specific gravity and end of discharge voltage.

[0281] Ideally, the change in specific gravity of the sulfuric acid in a battery cell over an extended number of cycles of the battery cell is minimized, because this indicates a reduction in stratification. The testing reflected in FIG. 32 was performed exclusively with the P-wrapped samples with 2 positive electrodes and 1 negative electrode therebetween (and, as a result, 2 P-wraps per sample), and a compression of approximately 20kPa. First, the specific gravity of the sulfuric acid in a control sample of an AGM separator was sampled at a predetermined interval between 0 and over 500 cycles and plotted on the graph of FIG. 32. The specific gravity of the sulfuric acid in a control sample including an uncoated separator 720 was sampled at a predetermined number of intervals between 0and over 600 cycles and plotted on the graph of FIG. 32. Next, the specific gravity of the sulfuric acid in a cell having separators 700 coated on the side proximate the negative electrode was sampled at a predetermined interval between 0 and 600 cycles and plotted on the graph of FIG. 32. Finally, the specific gravity of the sulfuric acid in a cell having separators 700 coated on the side proximate the positive electrode was sampled at a predetermined interval between 0 and 600 cycles and plotted on the graph of FIG. 32.

[0282] While the AGM separator control sample resulted in the least amount of change in specific gravity, it is clear that the sample having separators 700 coated on the sides proximate the positive electrodes led to less change in specific gravity through the tested number of cycles than both the uncoated sample and the sample coated on the sides proximate the negative electrode.

[0283] As previously described, the end of discharge voltage of a battery cell ideally remains constant over an extended number of cycles of the battery cell, because it ensures consistent performance and reliability of the battery, stabilizes open circuit voltages, prolongs its lifespan, and minimizes the risk of damage to connected devices or systems relying on the battery's power supply. The testing reflected in FIG. 33 used the same battery cells as those from FIG. 32. First, the average end of discharge voltage of a control sample of an AGM separator was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 33. The average end of discharge voltage of a control sample including an uncoated separator 720 was sampled at a predetermined number of intervals between 0 and over 1000 cycles and plotted on the graph of FIG. 33. Next, the average end of discharge voltage of a cell having a coated separator 724 coated on the side proximate the negative electrode was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 33. Finally, the average end of discharge voltage of a cell having a coated separator 724 coated on the side proximate the positive electrode was sampled at a predetermined interval between 0 and 1000 cycles and plotted on the graph of FIG. 33. While the AGM separator control sample resulted in the least amount of change / reduction in average end of discharge voltage over the cycles, it is clear that separators 700 coated on the sides proximate the positive electrodes led to less change / reduction in average end ofdischarge voltage through the tested number of cycles than both the uncoated sample and the sample coated on the sides proximate the negative electrode.Test 5Example 21 (AGM):

[0284] Example 21 is one or more AGM separators were provided and otherwise unmanipulated.Example 22 (“U250X” uncoated - control):

[0285] One or more uncoated separators 720 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween were prepared. The negative electrode plate was wrapped with the uncoated separator 720 so that the cross-ribs faced the negative plate and the other rib profile faced the positive plates. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. No coating was applied to the profiles of the uncoated separator 720.Example 23 (“U250X- single side coated”):

[0286] One or more coated separators 724 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. A coating was applied to the profiles of the coated separator 724 facing the negative plate. Example 24 (“U250X- double side coated”):

[0287] One or more coated separators 724 having profile 2 were provided and a cell with two positive electrode plates and one negative electrode plate therebetween was prepared. The negative electrode plate was wrapped with the coated separator 724 so that the cross-ribs faced the positive plates and the other rib profile faced the negative plate. In the battery cell, the cross-rib runs parallel to a top and bottom of the battery cell. The coating was applied to both profiles of the coated separator 724 facing both the negative and the positive plates.

[0288] FIG. 34 illustrates a graph of data obtained using a X which plots end of discharge voltage to number of cycles, in accordance with examples of the separator of the disclosure. Single-sided coated and double-sided coated separators 724 weresubjected to 17.5% PSOC cycling to collect end of discharge voltage for over 1500 cycles. These data were compared to the end of discharge voltage for the same number of cycles for an AGM separator and an uncoated separator 720. After approximately 1500 cycles, the end of discharge voltage of both coated separator samples 724 was approximately 2.0V, which is similar to that of the AGM separator. The uncoated separator 720 experienced a reduction in end of discharge voltage to approximately 1 ,98V. Clearly, by including a coating 712, the coated separators 724 a batter having performance similar to that of an AGM separator can be achieved.Example 25- Coated Gauntlet

[0289] A tubular battery was prepared by coating a gauntlet with a composition comprising a binder and a siliceous material. In some embodiments, a coated separator was also added.

[0290] FIG. 35 illustrates a graph of the stages of a charge test protocol, in accordance with examples of the separator of the disclosure. The test protocol may collect data such as charging efficiency and current. First, the battery cell is exposed to a constant current charge in Stage 1 . Then, in Stage 2, a topping charge is provided, followed by a float charge in stage 3 with a reduced current. For the testing of the present disclosure, the separators exposed to the test protocol of FIG. 35 were (i) a control of an uncoated separator 720, (ii) a single-sided coated separator 724, and (iii) a double-sided coated separator 724. FIG. 36 illustrates cross-sectional views of such separators subjected to the charge test protocol of FIG. 35, obtained by a Hirox Microscope. The coating is shown as well adhered and conformal to the substrate surface features and of a uniform thickness.

[0291] FIG. 37 illustrates a graph of data obtained during the test protocol outlined in FIG. 35, using a voltmeter which plots charge voltage to step time, in accordance with examples of the separator of the disclosure. As illustrated, both coated separator samples 724 exhibited appropriate charge voltages for step times comparable to those of the AGM separator, indicating no considerable loss in charging efficiency. FIG. 38 illustrates a graph of data obtained during the test protocol outlined in FIG. 35 obtained using a voltmeter which plots charge current to step time, in accordance with examplesof the separator of the disclosure. As illustrated in FIG. 38, both coated 720 and uncoated separator 724 examples maintained higher current in the float phase of the test protocol.

[0292] FIG. 39 illustrates a graph of data which plots puncture strength of the coated separator, in accordance with examples of the separator of the disclosure. The graph in FIG. 39 draws parallels, via puncture strength data, between different binder materials of the coating of the coated separator 724 and the resistance to oxidation of the coated separator 724. Binder A contains a monomer component having butyl acrylate and a- methyl styrene. Binder B is formaldehyde-free and would be cell tested as a candidate substitute for Binder A. Binder H contains a monomer component having styrene butadiene. As illustrated by the high puncture strength both before and after being subjected to charging cycles, Fig. 39, all but Binder F showed puncture strength equivalency or improvement over uncoated control.

[0293] FIG. 40 illustrate cross-sectional views of a 19X EFS (+) coated separator 724, obtained by a Hirox Microscope, before exposure to an acid with a specific gravity of 1 .1 , while. FIG. 41 illustrates the gelling of the coating after exposure to the sulfuric acid for 1 hour. The gelling is shown to be uniform at this specific gravity of 1 .1 .

[0294] FIG. 42 illustrate cross-sectional views of a 19X EFS (+) coated separator 724, obtained by a Hirox Microscope, before exposure to an acid with a specific gravity of 1 .2, while. FIG. 43 illustrates the gelling of the coating after exposure to the sulfuric acid for 1 hour. The gelling is shown to be uniform at this specific gravity of 1 .2.

[0295] FIG. 44 illustrates cross-sectional views of a 19X EFS (+) coated separator 724 obtained by a Hirox Microscope, before exposure to an acid with a specific gravity of 1 .3, while FIG. 45 illustrates the gelling of the coating after exposure to the sulfuric acid for 1 hour. The gelling is shown to be uniform at this specific gravity of 1 .3. Thus, the presently disclosed coated separator provides consistent and uniform swelling with acid at a range of specific gravities.

[0296] FIGS. 46-42 illustrate cross-sectional views of a first side of a LI250X profile double side coated separator 724, obtained by a Hirox Microscope, after prolonged 24- hour exposure to an acid with a specific gravity of 1.28, in accordance with examples of the coated separator 724 of the disclosure. Notably, in the orientation of the images ofFIGS. 46-42, the “U” profile side is at the top. The gelling is shown to be uniform at this specific gravity of 1 .28.

[0297] FIGS. 49-45 illustrate cross-sectional views of a second side of a U250X profile double side coated separator 724, obtained by a Hirox Microscope, after prolonged 24- hour exposure to an acid with a specific gravity of 1.28, in accordance with examples of the separator of the disclosure. Notably, in the orientation of the images of FIGS. 49-45, the “250X” profile side is at the top. The gelling is shown to also be uniform at this specific gravity of 1 .28.Rupture Testing BCS-21 Protocol

[0298] The “Rupture Test” is a standardized test method to determine the integrity of battery cells under specific conditions, the test method being derived from, and performed in accordance with, Section 9.0 of the Battery Council International “BCI Specification For ‘Non-Spillable Certification’ Valve Regulated Lead-Acid (VRLA) Batteries” test protocol, also referred to as “BCS-21”. To conduct the test, VRLA battery cells are prepared. Battery cells were prepared, each equipped with a separator selected from: an absorbent glass mat separator, an uncoated separator 720, a single “X” side coated separator 724, a single “U” side coated separator 724, and a doublesided coated separator 724. Each separator was captured within the battery cell with a “hand fit” compression of approximately 10%. Initially, the dry weight of each battery cell was determined, followed by filling them to capacity with sulfuric acid and recording their weights when full.

[0299] Following a resting period of at least 24 hours, the sulfuric acid from each cell was poured into separate containers, and the weight of the removed acid was measured. Subsequently, the weight of each cell after acid removal was recorded. A 5 Cycle test was then performed on each battery cell to ensure that its capacity remains at least 90% of its rated capacity.

[0300] After allowing the cells to sit for a minimum of one-hour post-charge, a slit was cut into the smaller side of the battery case, positioned 1 / 2 inches (1.27 cm) from the bottom and measuring 1 / 8 inches (0.3175 cm) thick. Alternatively, the length of the slit is to be 1 inch (2.54 cm) long or be at least 50% of the distance between the cell walls, whichever is smaller. The cells were then placed upright in glass dishes within an ovenset to 55 °C±1 , with a thermocouple monitoring the outer case temperature. Over the course of one hour, the temperature gradually reaches the desired level and is maintained for four hours.

[0301] Following the completion of the heating period, the Pyrex dishes were inspected for any spilled acid. Successful completion (“pass”) of the Rupture Test is demonstrated when no unabsorbed free-flowing liquid is present in the Pyrex dishes. Additionally, the battery cells, particularly around the slit area, and the collection tray were examined for any signs of leakage.

[0302] In a first round of the Rupture Test, one battery cell containing an absorbent glass mat, and one battery cell containing a double-sided coated separator 724 were prepared. The samples were subjected to the Rupture Test with a compression of approximately 10% with the following outcomes summarized in Tablel :TABLE 1 Rupture Testing under BCS-21 Protocol of Presently Disclosed Separator vs Control

[0303] In a second round of the Rupture Test with a compression of approximately 10%, one battery cell containing an uncoated “U250X” separator 720, one battery cell containing a single “U250X” “X” side coated separator 724, one battery cell containing a single “U250X” “U” side coated separator 724, and one battery cell containing a doublesided coated “U250X” separator 724 were prepared and tested. The above samples were subjected to the Rupture Test with the following results summarized in Table 2.TABLE. 2 Rupture Testing under BCS-21 Protocol of Presently Disclosed Separator vs Control

[0304] Results of each round of the Rupture Test indicate that the various coated separator configurations pass the requirements of the test. While the second round of testing indicates that a uncoated separator configuration, having a coating on a single side of a separator, either to the “X” side or the “II” side, did not pass. A double-sided coated separator configuration of the present disclosure provides even further improvement to the acid absorption characteristics of a battery cell, ands, the performance of battery cells equipped such with double-sided coated separators are comparable with those equipped with AGM separators.

[0305] Thus, as demonstrated in Tables 1 and 2, a lead acid battery using coated separator configurations as presently disclosed demonstrated at least a 66 weightpercent absorption of acidic electrolyte after a Rupture Test in accordance with, Section 9.0 of the Battery Council International “BCI Specification For ‘Non-Spillable Certification’ Valve Regulated Lead-Acid (VRLA) Batteries” (BCS-21 ) test protocol.

[0306] In one example, a flooded lead acid battery having performance closer to an AGM battery or a VRLA battery using the coated separator as presently disclosed is provided. A VRLA battery having performance closer to an AGM battery using the coated separator as presently disclosed is provided. In one example the aforementioned batteries have performance bridging flooded, VRLA-AGM and gelled batteries.

[0307] In one example, a lead acid battery using the coated separator as presently disclosed is a flooded battery or a valve-regulated lead acid (VRLA) battery.

[0308] In a flooded lead acid battery, an improvement comprising performance of at least 50% of a VRLA or gelled lead acid battery using the coated separator as presently disclosed is realized. In a VRLA or gelled lead acid battery, an improvement comprising performance of at least 50%, at least 60%, at least 70%, or at least 80% of a AGM lead acid battery using the coated separator as presently disclosed is also realized.

[0309] In a flooded lead acid battery, an improvement comprising performance of at least 80% of a VRLA or gelled lead acid battery using the coated separator as presently disclosed is realized. In a VRLA or gelled lead acid battery, an improvement comprising performance of at least 80% of a AGM lead acid battery using the coated separator as presently disclosed is also realized.

[0310] A lead acid battery using the coated separator as presently disclosed, where the siliceous material in the coating when applied to separator is swelled 10% to 70% by volume by acid electrolyte has been demonstrated to decrease a gap between the separator and an electrode. A lead acid battery using the coated separator as presently disclosed, where at least one of a thickness, a height, or a width of the coating when applied to the separator is swelled 10% to 70% by volume by acid electrolyte has been demonstrated decrease a gap between the separator and an electrode.

[0311] A lead acid battery using the coated separator as presently disclosed, is applicable to a flooded battery, or a valve-regulated lead acid (VRLA) battery, with or without an absorptive glass mat (AGM).

[0312] A lead acid battery using the coated separator as presently disclosed, has been demonstrated to provide at least two of the following: a cycle life between 500 and 1500 cycles at 80% depth of discharge (DOD); a stable voltage and an acid stratification of less than 0.06 specific gravity at 100 cycles measured vertically; or cost and / or manufacturability equivalent to that of a flooded lead acid battery. In one example, the cycle life is between 500 and 1500 cycles at 80% depth of discharge (DOD) and the acid stratification is less than 0.06 specific gravity measured vertically at 500 cycles.

[0313] A lead acid battery using the coated separator as presently disclosed, has been demonstrated to provide at least two of the following: a cycle life between 500 and 1500 cycles at 50% depth of discharge (DOD); maintain CCA (Cold Cranking Amps), RC (Reserve Capacity) and C20 rating performance while improving cycle life by at least 3X. A reserve capacity test measures how long a battery can continuously deliver a specific current (typically 25 amps) at a standard temperature (around 80°F) before its voltage drops to a predetermined level (usually 10.5 volts). The C20 rating is a standardized way to evaluate a battery's energy storage capability. In one example, the cycle life is between 500 and 1500 cycles at 50% depth of discharge (DOD) ; maintains CCA (Cold Cranking Amps), RC (Reserve Capacity) and C20 rating performance while improving cycle life by at least 3X.

[0314] In accordance with at least certain aspects, objects or embodiments, there is provided or disclosed a coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane is provided comprising a microporous substrate; and a coating on one or both sides of the microporous substrate. The coating comprises a polymeric binder and inorganic filler or siliceous material. In some examples, the separator is coated on one or both sides of the microporous substrate or membrane, wherein the coating comprises a polymeric binder, siliceous material, and carboxymethyl cellulose (CMC). In some examples, the microporous substrate may be a ribbed microporous substrate comprising polyethylene. Also provided are batteries including the coated battery separator, coated battery gelation composite substrate, or coated battery separator membrane. Such batteries may be improved flooded lead acid batteries, VRLA gel batteries, AGM batteries, storage batteries, or flow batteries.

[0315] In one example, a battery separator is provided, the separator comprising amicroporous substrate having a first side and an opposing second side, and a coating adjacent at least one of the first side and the opposing second side, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0316] In a preferred example a separator is provided oriented such that a major rib faces the negative active material (NAM) of a negative plate or electrode and a flat, minor rib, mini-rib, or cross-rib may face the positive active material (PAM) of a positive plate or electrode. This separator orientation is referred to herein as a reverse orientation as it is contrary to typical, historical or normal separator orientation in a lead acid battery where a major rib is provided next to the PAM and a flat, minor rib, mini-rib, or cross-rib is provided next to a NAM. The possibly preferred reverse orientation of the present disclosure or invention provides a large electrolyte and oxygen reservoir next to the NAM for sufficient recombination of H2O. The possibly preferred homogenous, consistent, uniform gelation layer formed form from a coating comprising a mixture of a polymeric binder and a siliceous material a or a silicious filler coated on a flat, minor rib, mini-rib, or cross-rib separator oriented to be in an intimate contact to the PAM by as much as 100% contact may address, reduce, eliminate or retard H2SO4 stratification.

[0317] In one preferred example, a battery separator is provided such that a separator comprising a microporous substrate having a first side with high surface contact “area” adjacent to the PAM and- or a second side with high surface contact “area” adjacent to the NAM on an opposing side. A coating adjacent at least one of the first side with high surface “area” and the opposing second side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0318] In one possibly most preferred example, a battery separator is provided such that a separator comprising a microporous substrate having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a flooded lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0319] In another possibly most preferred example, a battery separator is provided in a reverse orientation with the typical negative side ribs adjacent the PAM and the typical positive side ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to thePAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0320] In yet another possibly most preferred example, a lead acid battery separator is provided in a reverse orientation with the typical negative side minor ribs adjacent the PAM and the typical positive side major ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0321] In still yet another possibly most preferred example, a lead acid battery separator for a FLA, VRLA, VRLA-Gel, or VRLA-AGM cell, battery or system is provided in a reverse orientation with the typical negative side minor ribs adjacent the PAM and the typical positive side major ribs adjacent the NAM, such that the separator comprises a microporous substrate or membrane having a first side with high surface contact “area” adjacent to the PAM of a positive electrode in a lead acid battery and a coating adjacent at least the first side with high surface “area”, the coating comprising a mixture of a polymeric binder and a siliceous material.

[0322] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, or reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, surprisingly and unexpectedly may significantly extend the Partial State of Charge (PSoC) cycle life of FLA batteries by an impressive 500%.

[0323] Lead-acid batteries maintain a decisive cost advantage over lithium-ion, driven by a well-established U.S. manufacturing base, a robust recycling infrastructure, and a complete reliance on domestic materials and parts. This strategic position makes lead- acid a formidable player in the U.S. battery electric vehicle (BEV) market, where its roleas an auxiliary battery technology remains crucial. While lead-acid batteries typically last 5-8 years under normal conditions, far shorter than the purported 10-15-year lifespan of most BEV lithium-ion propulsion batteries, they must evolve to stay relevant. To remain competitive, lead-acid technology must enhance its performance and longevity, while continuing to leverage its unparalleled cost and domestic supply advantages.

[0324] Lead-acid batteries are particularly prone to acid stratification, especially during Partial State of Charge (PSoC) activities, which is typical of start-stop operation. Acid stratification occurs primarily during the charging cycle, when concentrated acid is released as a byproduct of the lead-acid reaction, mainly from the positive plate. This typically can be mitigated by fully charging, and overcharging the battery generating hydrogen / oxygen gas bubbles to rise and mix the electrolyte. However, these gas bubbles may be combustible, the gassing may cause acid to spew out of the container, and overcharging is seen as squandering useful energy. Should acid stratification be left unchecked, several other challenges will arise, including miscommunication with the Battery Management System (BMS), which monitors the battery's State of Health (SoH), as well as accelerated sulfation, ultimately reducing the battery’s cycle life.

[0325] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, or coated or treated silica filled polyethylene membranes, surprisingly and unexpectedly may be used in a reverse separator orientation for improving Partial State of Charge (PSoC) lead-acid battery performance. Briefly, the separator is traditionally oriented with the major ribs facing the positive plate (minor rib faces negative plate), allowing more acid to the otherwise acid-deficient positive plate. However, PSoC operation and this typical orientation may instead create an acid deficiency at the negative plate during its operation. By applying the inventive reverse separator orientation and placing the gelation coating or layer to the minor rib side against the NAM of the positive plate, the system becomes more effective. In this new configuration, the coating or layer in the presence of concentrated acid, will form a gelation network that encapsulates and holds the acid in place for subsequentreactions. The gelling, combined with slight compression (such as only 5%), pushes the separator up against the positive plate, preventing Positive Active Material (PAM) shedding and reducing the precipitation of concentrated acid. Additionally, having the major ribs facing the negative plate allows more acid to reach the negative plate, overcoming the previous acid deficiency. The free-flowing acid towards the negative plate, mitigates power loss often associated with fully gelled systems like Gel batteries. As a result, these synergistic effects surprisingly, unexpectedly, and favorably yielded a remarkable improvement in PSoC performance, achieving a 5 times enhancement in two standardized lifecycle tests — 17.5% PSoC and 50% Depth of Discharge (DoD) tests.

[0326] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, the novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, or coated or treated silica filled polyethylene membranes, surprisingly and unexpectedly may improve Flooded Lead Acid Batteries (FLB) to perform more like and compete with AGM batteries and may even improve Valve-Regulated Lead Acid Batteries (VRLA), VRLA-Gel Batteries and VRLA-AGM Batteries.

[0327] In accordance with at least certain aspects, objects or embodiments of the present disclosure or invention, a novel composite layer or coating is applied to a silica filled base PE Separator or membrane. When combined with a reverse separator orientation, this inventive approach may yield a remarkable 500% enhancement in Partial State of Charge (PSoC) cycle life performance. Specifically, by applying the gelation layer to the minor rib and inverting the orientation, the gelation layer faces the positive plate, forming a gelation network in the presence of acid. This network effectively immobilizes the generated, concentrated acid, facilitating subsequent reactions. Concurrently, slight compression (such as only 5%) pushes the separator against the positive plate, mitigating the shedding of Positive Active Material (PAM). The reverse orientation major ribs, now positioned against the negative plate, ensure adequate acid supply, overcoming acid deficiency. This synergistic approach has demonstrated a remarkable 5x improvement in PSoC performance across two standardized life-cycle tests: 17.5% PSoC and 50% Depth of Discharge (DoD) tests.

[0328] Recognizing the promising results of this new technology, Daramic, LLC of Charlotte, NC has been selected as a collaborator for a US Department of Energy (DOE) project focused on developing improved 12V Lead Acid Batteries for Safety Critical Electric Vehicle Applicationsaimed to address the critical need for enhanced 12V auxiliary battery performance in the growing electric vehicle market.

[0329] Since the advent of Battery Electric Vehicles (BEVs), a 12V auxiliary (AUX) battery has been an indispensable component of the vehicle's electrical system. While lithium-ion batteries are occasionally employed, lead acid batteries remain the most cost-effective solution for this critical function. The U.S. lead acid battery industry boasts a mature and robust manufacturing base, with a recycling rate exceeding 99% and minimal reliance on foreign materials. These factors solidify the position of lead acid batteries as the preferred AUX battery technology for the burgeoning U.S. BEV market.

[0330] A significant challenge in extending the service life of enhanced flooded lead acid batteries (EFB) auxiliary batteries is the detrimental effects of cycling, primarily sulfation of the negative plate due to acid stratification and the shedding / wear and tear of the positive plate. Acid stratification elevates the open-circuit voltage, misleading the Battery Management System (BMS) into undercharging the battery, ultimately leading to premature failure. As previously discussed, Daramic's innovative new gelation layer or coating separator technology, featuring a microporous polyethylene separator with a gelation composite layer, effectively addresses this issue. By absorbing and immobilizing the electrolyte, the gelation layer (preferably against the PAM, with major ribs against the NAM) significantly mitigates acid stratification and consequently enhances PSoC cycle life.

[0331] In at least one aspect, object or embodiment, the microporous substrate, separator, or separator membrane is shaped to receive an electrode of a battery such as a lead acid battery or FLA. For example, the microporous substrate, separator, or separator membrane may be a wrap, a V or U, a sleeve, a gauntlet, an envelope or pocket, a hybrid envelope or pocket with slits or openings (in the base, seams, and / or sides), a positive electrode envelope (“positive enveloping separator” or “P-wrapped”), a negative electrode envelope (“negative enveloping separator” or “N-wrapped”), may be a folded or have a sealed crease edge, the lateral edges may be continuously or intermittently sealed seam edges, the edges may be bonded or sealed by adhesive, heat, ultrasonic welding, and / or the like, or any combination thereof.

[0332] In at least one possibly preferred aspect, object or embodiment, the microporous substrate, separator, or separator membrane is a reverse oriented microporous substrate, separator, or separator membrane shaped to receive an electrode of a battery such as a lead acid battery or FLA. For example, the reverse orientatedmicroporous substrate, separator, or separator membrane may be a wrap, a V or II, a sleeve, a gauntlet, an envelope or pocket, a hybrid envelope or pocket with slits or openings (in the base, seams, and / or sides), a positive electrode envelope (“positive enveloping separator” or “P-wrapped”), a negative electrode envelope (“negative enveloping separator” or “N-wrapped”), may be a folded or have a sealed crease edge, the lateral edges may be continuously or intermittently sealed seam edges, the edges may be bonded or sealed by adhesive, heat, ultrasonic welding, and / or the like, or any combination thereof.

[0333] Unless stated otherwise, the separator testing procedures are typical LAB separator tests such as BCI tests found in the BCI Battery Test Manual BCIS-03B Rev Jan-18.

[0334] A typical chart showing the cycle life performance of AGM batteries would demonstrate that with a 50% depth of discharge (DoD), an AGM battery can last for around 500-1000 cycles, while a deeper discharge at 80% DoD would significantly shorten its lifespan to around 200-500 cycles; essentially, the deeper the discharge, the fewer cycles the battery can endure before reaching the end of its life.

[0335] A typical AGM cycle life performance graph may show a steep decline in cycle life as the depth of discharge (DoD) increases, indicating that the more deeply an AGM battery is discharged, the fewer charge cycles it can endure before reaching the end of its useful life; with the optimal cycle life occurring at a moderate DoD level, usually around 50% discharge, and significantly reduced lifespan when discharging beyond 80%.

[0336] Although many examples of the present disclosure have just been described above, the present disclosure may be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these examples are provided so that this disclosure will satisfy applicable legal requirements. Also, it will be understood that, where possible, any of the advantages, features, functions, devices, and / or operational aspects of any of the examples of the present disclosure described and / or contemplated herein may be included in any of the other examples of the present disclosure described and / or contemplated herein, and / or vice versa. In addition, where possible, any terms expressed in the singular form herein are meant to also include the plural form and / or vice versa, unless explicitly stated otherwise. Accordingly, the terms“a” and / or “an” shall mean “one or more,” even though the phrase “one or more” is also used herein. Like numbers refer to like elements throughout.

[0337] While certain exemplary examples have been described and shown in the accompanying drawings, it is to be understood that such examples are merely illustrative of, and not restrictive on, the broad disclosure, and that this disclosure not be limited to the specific constructions and arrangements shown and described, since various other changes, combinations, omissions, modifications and substitutions, in addition to those set forth in the above paragraphs, are possible. Those skilled in the art will appreciate that various adaptations and modifications of the just described examples can be configured without departing from the scope and spirit of the disclosure. Therefore, it is to be understood that, within the scope of the appended claims, the disclosure may be practiced other than as specifically described herein.

Claims

WHAT IS CLAIMED IS:1 . A battery separator comprising: a microporous substrate having a first side and an opposing second side; and a coating adjacent at least one of the first side and the opposing second side; the coating comprising a mixture of a polymeric binder and a siliceous material.

2. The battery separator of claim 1 , wherein the microporous substrate is shaped to receive an electrode of a battery.

3. The battery separator of any one of the previous claims, wherein the microporous substrate is configured as a sheet or rolled sheet of between 25 to 4000 micron thickness.

4. The battery separator of any one of the previous claims, wherein the microporous substrate is a polyolefin membrane, a filled polyolefin porous membrane, a glass mat, an absorptive glass mat (AGM), a woven, a non-woven, a PVC membrane, a phenolic membrane, a cellulosic derivative, or combinations thereof.

5. The battery separator of any one of the previous claims, wherein the microporous substrate is filled with at least filler of silica, synthetic wood pulp (“SWP”), lignins, glass fibers, synthetic fibers, cellulosic fibers, fishbone meal, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, clay, aluminum silicate, sodium aluminum silicate, aluminum polysilicate, alumina silica gels, glass particles, carbon black, activated carbon, carbon fibers, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, lead oxide, tungsten, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate, magnesium carbonate, 5-20 weight percent aromatic oil, pigment, additives, and combinations thereof.

6. The battery separator of any one of the previous claims, wherein the microporous substrate is a filled polyolefin porous membrane that comprises at least one filler and a weight ratio of the at least one filler to polyolefin from 2.5:1 .0 to 5.0:1 .0.

7. The battery separator of any one of the previous claims, wherein the coating is positioned on the at least one of the first side and the opposing second side.

8. The battery separator of any one of the previous claims, wherein the coating is directly adjacent the at least one of the first side and the opposing second side.

9. The battery separator of any one of the previous claims, wherein at least one of the first side or the opposing second side comprises ribs, protrusions, dimples, or combinations thereof, wherein, when present, the ribs or protrusions are continuous, discontinuous, longitudinally extending, latitudinally extending, diagonally extending, angled, zig-zagged, or combinations thereof.

10. The battery separator of claim 9, wherein the ribs are on the first side and the protrusions are on the opposing side.11 . The battery separator of any one of claims 9 or 10, wherein the coating contours the ribs or protrusions and / or provides indentations or channels therein.

12. The battery separator of any one of claims 9 to 11 , wherein the ribs or protrusions extend from a backweb and the coating at least covers or contours the backweb between the ribs or protrusions.

13. The battery separator of any one of the previous claims, wherein the separator is at least partially ionically conductive when exposed to sulfuric acid of Specific Gravity of at least 1 .0.

14. The battery separator of any one of the previous claims, wherein the coating is an aqueous emulsion of at least the polymer binder and the siliceous material.

15. The battery separator of any one of the previous claims, wherein the coating comprises an emulsifier, an ionic surfactant, a cationic surfactant, additives, or combinations thereof.

16. The battery separator of claim 14 or 15, wherein the emulsifier is at least one of alkyl benzene sulfonate, polyethylene glycol (PEG), polypropylene glycol (PPG), alkyl sulfate, polyoxyethylene alkyl ether, and alkyl sulfonate.

17. The battery separator of any one of the previous claims, wherein the weight ratio of the polymeric binder to the siliceous material is from 1 :2 to 1 : 10.

18. The battery separator of any one of the previous claims, wherein the polymeric binder is a non-elastomeric polymer.

19. The battery separator of any one of the previous claims, wherein the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, or blends or grafts thereof.

20. The battery separator of claim 19, wherein the cellulosic derivative is carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose.21 . The battery separator of any one of the previous claims, wherein the polymeric binder is an elastomeric polymer combined with a cellulosic derivative, or a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose.

22. The battery separator of any one of the previous claims, wherein the polymeric binder is a mixture of a polymer, siliceous material, and a cellulosic derivative in a weight ratio of from 1 :2:0.1 to 1 : 10:0.5.

23. The battery separator of any one of the previous claims, wherein the polymeric binder is dried, cured or crosslinked.

24. The battery separator of any one of the previous claims, wherein the siliceous material is a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

25. The battery separator of any one of the previous claims, wherein the volume of the siliceous material in the coating is configured to swell about 25 volume percent to about 70 volume percent when contacted with sulfuric acid.

26. The battery separator of any one of the previous claims, wherein at least one of a thickness, a height, or a width of the coating is configured to swell about 25 volume percent to about 70 volume percent when contacted with sulfuric acid.

27. A lead acid battery comprising the separator of any one of the previous claims.

28. A lead acid battery comprising the separator of any of claims 1 to 26, wherein the siliceous material in the coating is swelled 25 % to 70% by volume by acid electrolyte so as to decrease a gap between the separator and an electrode.

29. A lead acid battery comprising the separator of any of claims 1 to 26, wherein at least one of a thickness, a height, or a width of the coating is swelled 25 % to 70% by volume by acid electrolyte so as to decrease a gap between the separator and an electrode.

30. A lead acid battery comprising the separator any of claims 1 to 26, wherein the battery is a flooded battery, or a valve-regulated lead acid (VRLA) battery, with or without an absorptive glass mat (AGM).31 . A lead acid battery comprising the separator of any of claims 1 to 26, wherein the separator provides at least 66 weight percent absorption of acidic electrolyte after a Rupture Test in accordance with, Section 9.0 of the Battery Council International “BCI Specification For ‘Non-Spillable Certification’ Valve Regulated Lead- Acid (VRLA) Batteries” (BCS-21 ) test protocol.

32. A lead acid battery comprising the separator of any of claims 1 to 26, wherein the battery provides at least two of the following: a cycle life between 500 and 1500 cycles at 50% depth of discharge (DOD); maintain CCA, RC, and C20 rating while improving cycle life by at least 3X; - or cost and / or manufacturability equivalent to that of a flooded lead acid battery.

33. The lead acid battery of claim 32, wherein the cycle life is between 500 and 1500 cycles at 50% depth of discharge (DOD) and CCA , RC, and C20 rating maintained while improving cycle life by at least 3X.

34. In a flooded lead acid battery, the improvement comprising performance of at least 80% of a VRLA or gel lead acid battery using the separator any of claims 1 to 26.

35. In a VRLA or gelled lead acid battery, the improvement comprising performance of at least 80% of a AGM lead acid battery using the separator any of claims 1 to 26.

36. A method of manufacturing a lead acid battery, comprising:filling the free lead acid battery with an electrolyte, the lead acid battery comprising a separator according to any of claims 1 to 26 positioned between a positive and a negative electrode; sealing the filled lead acid battery; and providing a filled lead acid battery; wherein the filling is completed without the use of a vacuum.

37. The method of claim 36, wherein the lead acid battery is a maintenance- free battery.

38. The method of any one of claims 36-37, wherein the filling is completed in less than four minutes.

39. The method of any one of claims 36-38, wherein the filling is completed in three minutes or less.

40. A method of reducing acid stratification within a lead acid battery, the method comprising: filling a lead acid battery with electrolyte, the maintenance-free lead acid battery comprising a positive and a negative electrode and a separator therebetween, the separator comprising a coating comprising a polymeric binder and a siliceous material; introducing an electrolyte to the coating; swelling the siliceous material 25 10% to 70% by volume so as to decrease a gap between the separator and at least one of the positive electrode and the negative electrode; and reducing acid stratification within the lead acid battery.41 . The method of claim 40, wherein the lead acid battery is a maintenance- free lead acid battery.

42. The method of any one of claims 40-41 , wherein the filling is completed without the use of a vacuum.

43. The method of any one of claims 40-42, wherein the lead acid battery is a maintenance free battery.

44. The method of any one of claims 40-43, wherein the lead acid battery is a flooded lead battery or a valve-regulated lead acid (VRLA) battery, with or without an absorptive glass mat (AGM).

45. The method of any one of claims 40-44, wherein the separator is a polyolefin membrane, a filled polyolefin porous membrane, a glass mat, an absorptive glass mat (AGM), a woven, a non-woven, a PVC membrane, a phenolic membrane, a cellulosic, or combinations thereof.

46. The method of any one of claims 40-45, wherein the polymeric binder is a non-elastomeric polymer.

47. The method of any one of claims 40-46, wherein the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, an elastomeric polymer combined with a cellulosic derivative, a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose, or blends or grafts thereof.

48. The method of any one of claims 40-47, wherein the filler is a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

49. The method of any one of claims 40-48, wherein the electrolyte is sulfuric acid electrolyte.

50. A method of manufacturing a battery separator comprising: introducing a coating to at least one surface of a microporous substrate, the coating comprising a mixture of a polymeric binder and a siliceous material; and drying, crosslinking or curing the coating.51 . The method of clam 50, wherein, prior to the introducing step, the microporous substrate is primed, flame treated, plasma treated, or contacted with an adhesion promoter.

52. The method of any one of claims 50-51 , wherein the coating is an aqueous emulsion or slurry of the polymeric binder and the siliceous material.

53. The method of any one of claims 50-52, wherein the aqueous emulsion or slurry comprises an emulsifier, an ionic surfactant, a cationic surfactant, or combinations thereof, wherein the emulsifier is at least one of alkyl benzene sulfonate, polyethylene glycol (PEG), polypropylene glycol (PPG), alkyl sulfate, polyoxyethylene alkyl ether, and alkyl sulfonate.

54. The method of any one of claims 50-53, wherein the polymeric binder is a non-elastomeric polymer.

55. The method of any one of claims 50-54, wherein the polymeric binder is an acrylate, a methacrylate, a styrene, a cellulosic derivative, a polyurethane, a polyurethane-urea, an elastomeric polymer combined with a cellulosic derivative, a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose, or blends or grafts thereof.

56. The method of claim 55, wherein the cellulosic derivative is carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose.

57. The method of any one of claims 50-56, wherein the siliceous material is hydrophobic silica, fumed silica, precipitated silica, montmorillonite, chemically modified silica, or combinations thereof.

58. The method of any one of claims 50-57, wherein the siliceous material is present at 1 to 10 weight percent relative to the weight percent of the polymeric binder.

59. The method of any one of claims 50-58, wherein the polymeric binder is a mixture of a non-elastomeric polymer or elastomeric polymer, siliceous material, and a cellulosic derivative in a weight ratio of from 1 :2:0.1 to 1 : 10:0.5.

60. The method of any one of claims 50-59, wherein the coating comprises a crosslinking agent.61 . The method of any one of claims 50-60, wherein, during the drying or curing step, the coating is crosslinked.

62. The method of any one of claims 50-61 , comprising the use of processing aids and wherein the processing aids comprise one or more of emulsifiers, surfactants, anti-foaming agents, adhesion promoters, antioxidants, UV stabilizers, curing aids, and crosslinking agents.

63. The method of any one of claims 50-62 comprising introducing a coating to at least one surface of a microporous substrate and optionally, wherein, prior to the introducing step, embossing the microporous substrate on the at least one surface or on both surfaces.

64. The method of claim 63, wherein, prior to the introducing step, embossing the microporous substrate on both surfaces with the same or different profile or pattern.

65. The method of any one of claims 63-64, wherein, prior to the introducing step, embossing the microporous substrate on both surfaces with the same or differentpattern of ribs, protrusions, dimples, or combinations thereof, wherein, the ribs or protrusions are continuous, discontinuous, longitudinally extending, latitudinally extending, diagonally extending, or combinations thereof.

66. The method of claim 65, wherein the ribs or protrusions extend from a backweb and the coating at least covers the backweb between the ribs or protrusions.

67. The method of any one of claims 50-66, further comprising shaping the separator to receive an electrode of a battery.68 A coating formulation for a battery separator, the coating formulation comprising: a polymeric binder; an inorganic filler; and a remainder of aqueous media and processing aids.

69. The coating formulation of claim 68, wherein the polymeric binder is a non-elastomeric polymer.

70. The coating formulation of any one of claims 68-69, wherein the polymeric binder is an acrylate, a methacrylate, a styrene, a polyurethane, a polyurethane-urea, a cellulosic derivative, an elastomeric polymer combined with a cellulosic derivative, a styrene-butadiene rubber combined with carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose, or blends or grafts thereof.71 . The coating formulation of any one of claims 68-70, wherein the inorganic filler is a siliceous material.

72. The coating formulation of any one of claims 68-71 , wherein the siliceous material is at least one of a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, mixtures of two or more thereof, or a combination thereof.

73. The coating formulation of any one of claims 68-72, wherein the inorganic filler is present at 1 to 10 weight percent relative to the weight percent of the polymeric binder.

74. The coating formulation of any one of claims 68-73, comprising the use of processing aids and wherein the processing aids comprise one or more of emulsifiers, surfactants, anti-foaming agents, adhesion promoters, antioxidants, UV stabilizers, curing aids, and crosslinking agents.

75. The coating formulation of any one of claims 68-74, wherein the coating formulation is an aqueous emulsion.

76. A system comprising: at least one battery cell comprising an electrode plate; a separator pocketing the electrode plate, or adjacent the electrode plate; the separator comprising a coating, the coating comprising a mixture of a polymeric binder and inorganic filler; wherein the inorganic filler is configured to swell upon contact with acid; wherein the system provides performance of at least 80 percent of that of a AGM battery or gelled battery without the separator; or wherein the separator provides at least 66 weight percent absorption of acidic electrolyte after a Rupture Test in accordance with, Section 9.0 of the Battery Council International “BCI Specification For ‘Non-Spillable Certification’ Valve Regulated Lead- Acid (VRLA) Batteries” (BCS-21 ) test protocol.

77. The system of claim 76, wherein the polymeric binder is a non-elastomeric polymer.

78. The system of any one of claims 76-77, wherein the polymeric binder is an acrylate, a methacrylate, a styrene, a polyurethane, a polyurethane-urea, a cellulosic derivative, an elastomeric polymer in combination with a cellulosic derivative, or blends or grafts thereof.

79. The system of any one of claims 76-78, wherein the inorganic filler is a siliceous material.

80. The system of any one of claims 76-79, wherein the siliceous material is at least one of a hydrophobic silica, a fumed silica, a precipitated silica, a montmorillonite clay, a chemically modified silica, a mixture of two or more thereof, or a combination thereof.81 . The system of any one of claims 76-80, wherein the inorganic filler is present at 1 to 10 weight percent relative to the weight percent of the polymeric binder.

82. An internal combustion engine (ICE), hybrid, or electric vehicle comprising at least one battery, the at least one battery comprising: two or more electrodes; a separator positioned between the two or more electrodes, the separator coated with a mixture of a polymeric binder and a siliceous material; wherein the separator comprises a polyolefin membrane, a filled polyolefin porous membrane, a glass mat, an absorptive glass mat (AGM), a woven, a non-woven, a PVC membrane, a phenolic membrane, or combinations thereof; wherein the polymeric binder comprises a non-elastomeric polymer; wherein the siliceous material comprises hydrophobic silica, fumed silica, precipitated silica, montmorillonite, chemically modified silica, or combination thereof; and an electrolyte a least partially absorbed by the siliceous material.

83. A flooded lead acid battery having performance closer to an AGM battery using the separator of any of the above claims.

84. A flooded lead acid battery having performance closer to a Gel or gelled battery using the separator of any of claims 1 to 26.

85. The batteries of claims 83 or 84, having performance bridging flooded, VRLA-AGM and VRLA-Gel batteries.

86. A lead acid battery comprising the separator of any one of the previous claims, wherein the battery is a flooded battery or a valve-regulated lead acid (VRLA) battery.

87. The method of any one of claims 40-43, wherein the lead acid battery is a flooded lead battery or a valve-regulated lead acid (VRLA) battery.

88. The lead acid battery of claim 27, wherein the lead acid battery is a tubular lead acid battery comprising a gauntlet in addition to the separator, and wherein the gauntlet is coated with a coating comprising a mixture of a polymeric binder and a siliceous material.

89. A tubular lead acid battery comprising a separator and a gauntlet, wherein the gauntlet is coated with a coating comprising a mixture of a polymeric binder and a siliceous material.

90. The battery separator of any of claims 1 to 26, wherein the battery separator has a reverse orientation such that a major rib faces the negative active material (NAM) of a negative plate or electrode and a flat, planar, minor rib, mini-rib, or cross-rib faces the positive active material (PAM) of a positive plate or electrode, and the coating is on or adjacent the side of the microporous substrate facing the PAM.91 . The battery of any of claims 27 to 35, 82-86, 88, or 89, wherein the battery separator has a reverse orientation such that a major rib faces the negative active material (NAM) of a negative plate or electrode and a flat, planar, minor rib, mini-rib, orcross-rib faces the positive active material (PAM) of a positive plate or electrode, and the coating is on or adjacent the side of the microporous substrate facing the PAM_92. Novel or improved coated battery separators, coated battery gelation composite substrates, coated battery separator membranes, coated or treated polyolefin membranes, coated or treated silica filled polyethylene membranes, coated or treated silica filled polyethylene membranes with ribs on at least one side, coated or treated silica filled polyethylene membranes with ribs on both sides, reverse oriented coated or treated silica filled polyethylene membranes with ribs on both sides, related methods, and / or cells, batteries or systems incorporating the same as shown or described herein.

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