Lead-acid battery containing fibrous mat

Abstract

To provide a new battery separator and / or battery technology to prevent or impede the shedding of active material from electrodes in enhanced flooded lead acid batteries.SOLUTION: A flooded lead acid battery comprises an electrode array, comprising one or more negative plates and one or more positive plates alternately arranged and interleaved with one another. In some embodiments, a negative plate is wrapped with or enveloped in a fibrous mat, and an adjacent positive electrode is wrapped with or enveloped in a porous membrane. The fibrous mat is at least partially integrated into the negative plate. Either the negative plate with the fibrous mat at least partially integrated therein or an adjacent positive plate is enveloped in the porous membrane.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Cross-reference of related patent applications This application claims priority and interest to concurrently pending French patent application No. 1853502, filed on April 20, 2018, which is fully incorporated herein by reference.

[0002] According to at least selected embodiments, the Disclosure or Invention relates to novel or improved separators, battery separators, liquid battery separators, reinforced liquid battery separators, fibrous mats, batteries, cells, and / or methods for manufacturing and / or using such separators, battery separators, fibrous mats, liquid battery separators, reinforced liquid battery separators, cells, and / or batteries. According to at least certain embodiments, the Disclosure or Invention relates to novel or improved reinforced liquid battery separators, fibrous mats, liquid batteries for deep cycle applications, liquid batteries for power applications, liquid batteries for partially charged (PSoC) applications, and / or reinforced liquid batteries, and / or systems, vehicles, etc., including such separators, fibrous mats, and batteries, and / or improved methods for manufacturing and / or using such improved separators, fibrous mats, cells, batteries, systems, vehicles, etc. According to at least certain embodiments, the Disclosure or Invention relates to improved separators for enhanced liquid-type batteries, and / or improved methods for manufacturing and / or using such batteries having such improved separators. According to at least selected embodiments, the Disclosure or Invention relates to separators, in particular separators for enhanced liquid-type batteries having reduced electrical resistance and / or increased cold cranking amplifier. Also disclosed herein are methods, systems, and battery separators for improving active material retention, improving battery life, reducing moisture loss, reducing internal resistance, increasing wetting properties, reducing acid layering, improving acid diffusion, improving cold cranking amplifier, and improving uniformity, at least in enhanced liquid-type batteries. According to at least certain embodiments, the present disclosure or invention relates to an improved separator for an enhanced liquid cell, comprising one or more performance-enhancing additives or coatings, optimized porosity, optimized porosity, amorphous silica, highly oil-absorbing silica, highly silanol-group silica, retention of active material in electrodes and / or improved retention, and / or any combination thereof.

[0003] According to at least selected embodiments, the Disclosure or Invention relates to lead-acid batteries, particularly liquid lead-acid batteries, and separators for various lead-acid batteries, such as liquid lead-acid batteries or enhanced liquid lead-acid batteries, having the above. According to at least selected embodiments, the Disclosure or Invention relates to novel or improved separators, cells, batteries, and / or methods for manufacturing and / or using such separators, cells, and / or batteries. According to at least certain specific embodiments, the Disclosure or Invention relates to improved separators for lead-acid batteries, and / or improved methods for using such batteries having such improved separators. Furthermore, methods, systems, and battery separators for improving active material retention, battery life, battery failure, moisture loss, oxidation stability, float current, maintenance, and / or reduction, end-of-charge (EOC) current, the current and / or voltage required to charge and / or fully charge a deep-cycle battery are disclosed herein. The disclosed separator is useful in deep-cycle applications in, for example, prime movers or vehicles, and / or stationary machinery or vehicles, such as golf carts (also known as "golf carts"), fork trucks, inverters, renewable energy systems and / or alternative energy systems, such as, to name just a few, photovoltaic and wind power systems; in particular, the disclosed separator is useful in battery systems in which deep-cycle and / or partial-charge operation is part of the battery life, and more specifically, in battery systems in which additives and / or alloys (e.g., antimony (Sb)) are added to the battery to improve the battery life and / or performance, and / or the battery's ability to operate in deep-cycle and / or partial-charge states.

[0004] According to at least selected embodiments, the Disclosure covers improved lead-acid batteries, such as liquid lead-acid batteries, lead-acid batteries, and / or improved systems including battery separators, improved battery separators, improved vehicles including such systems, methods of manufacture or use, or combinations thereof. According to at least certain embodiments, the Disclosure or Invention covers novel or improved liquid lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacture, testing, and use of such improved liquid lead-acid batteries, and / or combinations thereof. Also disclosed herein are methods, systems, batteries, and / or battery separators for reducing oxidation and improving battery life and performance in liquid lead-acid batteries and in batteries operating in a partially charged state. [Background technology]

[0005] A battery separator electrically separates the positive and negative electrodes or positive and negative electrode plates of a battery to prevent electrical short circuits. Such a battery separator is typically microporous and ionically conductive so that ions can pass between the positive and negative electrodes or between the positive and negative electrode plates. The separator may be made of polyolefin, such as polyethylene. In lead-acid batteries, such as automotive batteries and / or industrial batteries and / or deep-cycle batteries, the battery separator is typically a microporous polyethylene separator; in some cases, such a separator may include a back web and a number of ribs present on one or both sides of the back web. See Non-Patent Document 1 below.

[0006] Enhanced Liquid-Based (EFB) and Absorbent Glass Mat (AGM) batteries have been developed to meet the growing demand for power sources in idle-start-stop (ISS) applications. EFB systems have a structure similar to conventional liquid-based lead-acid batteries, where the positive and / or negative electrodes are immersed in a liquid electrolyte surrounded by a microporous separator. AGM systems, on the other hand, do not contain a free liquid electrolyte. Instead, the electrolyte is absorbed within a glass fiber mat layered on the electrodes. Historically, AGM systems have been associated with higher discharge power, better cycle life, and greater cold-cranking amplification than liquid-based battery systems. However, AGM batteries are considerably more expensive to manufacture and more sensitive to overcharging. Therefore, EFB systems remain an attractive option for mobile and stationary power sources in a variety of markets and applications.

[0007] An EFB system may include one or more battery separators that separate or isolate the positive electrode from the negative electrode within a lead-acid battery cell. The battery separator may have two main functions: It must physically keep the positive electrode separate from the negative electrode to prevent any current passing between the two electrodes that could cause an electrical short circuit; and it must allow ionic current between the positive and negative electrodes with minimal resistance. While battery separators may be made of many different materials, these two conflicting functions have been well met by battery separators made of porous nonconductors. In this structure, the pores contribute to ion diffusion between the electrodes, and the non-conductive polymer network prevents electronic short circuits.

[0008] EFBs with increased discharge rate and cold cranking amperage or amperage ("CCA") may be able to replace AGM batteries. Cold cranking amperage is related to the internal resistance of the battery. A decrease in the internal resistance of enhanced liquid-electrolyte batteries is expected to increase the CCA rating. Therefore, there is a need for new battery separators and / or battery technologies to address and overcome the challenges arising from current lead-acid battery systems, particularly in enhanced liquid-electrolyte batteries, by reducing internal resistance and increasing cold cranking amperage.

[0009] To reduce fuel consumption and exhaust emissions, automakers have implemented various degrees of electric hybridization. One form of hybrid electric vehicle ("HEV") is sometimes referred to as a "micro HEV" or "micro hybrid." In such a micro HEV or similar vehicle, the vehicle may have an idle start-stop function that allows the engine to stop at various points during idle start-stop ("ISS") and / or regenerative braking. This increases the vehicle's fuel efficiency, but it also increases the burden on the battery, as it must supply power to auxiliary devices (e.g., air conditioning, media player, etc.) while the vehicle is not moving.

[0010] Conventional vehicles (e.g., cars without start-stop functionality) may use conventional liquid lead-acid batteries, such as start-light-ignition ("SLI") lead-acid batteries. Since the engine never stops during use, power is simply drawn from the battery when the engine is cranked or started. Therefore, the battery is typically in an overcharged state rather than a partially charged state. For example, such conventional liquid lead-acid batteries are often overcharged, and may be in a charged state of over 95%, over 96%, over 97%, over 98%, over 99%, or even over 100%. Overcharging causes bubbles (e.g., hydrogen bubbles) to form in the conventional lead-acid battery, and these circulating bubbles act to mix the liquid electrolyte (e.g., sulfuric acid) within the battery.

[0011] On the other hand, ISS vehicles are always in a partially charged state because they continuously draw power from the battery. In a partially charged state, no bubbles are generated, and the internal mixing of the electrolyte is substantially reduced, leading to oxidation within the battery. Thus, oxidation becomes a problem in various enhanced liquid-type batteries that operate in a partially charged state, such as idle-start-stop liquid lead-acid batteries. On the other hand, oxidation is not a problem at all in more conventional or standard liquid lead-acid batteries that are operated in an overcharged, fully charged, or nearly fully charged state.

[0012] Acidification is a term relating to the layering process in which water and sulfuric acid in the electrolyte concentrate at the bottom of the battery, resulting in a higher concentration of sulfuric acid at the top of the battery, and a correspondingly higher concentration of water at the top. Acidification is undesirable in liquid lead-acid batteries, such as enhanced liquid lead-acid batteries or start / stop liquid lead-acid batteries. Reduced acid levels at the top of the electrodes can impair uniformity and charge tolerance within the battery system, and can increase variations in internal resistance along the height of the battery from top to bottom. Increased acid levels at the bottom of the battery can artificially increase the battery voltage, potentially interfering with the battery management system and sending unintended / false health signal conditions to the battery management system. Overall, acidification results in higher resistance along the portion of the battery, which can lead to electrode problems and / or a shorter battery life. Given that start / stop batteries and / or other enhanced liquid lead-acid batteries are expected to become increasingly prevalent with hybrid and all-electric vehicles that increase vehicle fuel efficiency and reduce emissions, solutions to reduce acid layering and / or improve acid mixing are greatly needed.

[0013] In some cases, acid layering is performed in valve-controlled lead-acid batteries where the acid is immobilized by either a gelled electrolyte and / or an absorbent glass mat ("AGM") battery separator system. This can be somewhat mitigated by using acid-based lead-acid ("VRLA") technology. In contrast to the free-flowing electrolyte in liquid lead-acid batteries, the electrolyte in VRLA AGM batteries is absorbed in fibrous or fibrous materials, such as glass fiber mats, polymer fiber mats, or gelled electrolytes. However, VRLA AGM battery systems are substantially more expensive to manufacture than liquid battery systems. In some cases, VRLA AGM technology may be more sensitive to overcharging, may dry completely at high temperatures, may experience a gradual decrease in capacity, and may have a lower specific energy. Similarly, in some cases, gel VRLA technology may have a higher internal resistance and reduced charge tolerance. [Prior art documents] [Non-patent literature]

[0014] [Non-Patent Document 1] Besenhard, JO, Editor, Handbook of Battery Materials, Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), ch.9, pp.245-292 [Overview of the Initiative] [Problems that the invention aims to solve]

[0015] In an EFB system, the electrodes or plates consist of a lead alloy grid and an active material. During the manufacturing process of such an EFB, an active material paste is applied to the lead alloy grid and hardened to form the electrodes or plates. The paste may contain one or more of the following: carbon black, barium sulfate, lignosulfonate, sulfuric acid, and water. The hardening process transforms the paste into a mixture of lead sulfate, which becomes the electrically active material during the initial charge of the battery. The paste at the positive electrode is known as the positive electrode active material ("PAM"). Similarly, the active material at the negative electrode is known as the negative electrode active material ("NAM"). During the charge-discharge cycle of the battery, the electrodes experience expansion and contraction. Over time, this deformation of the electrodes causes the active material to detach from the electrodes and physically separate. As more and more active material detaches from the electrodes, the electrodes become ineffective, reducing the performance and lifespan of the battery. Therefore, there is a need for new battery separators and / or battery technologies to address and overcome the challenges arising from current lead-acid battery systems, particularly to prevent or inhibit the detachment of active material from electrodes in enhanced liquid lead-acid batteries.

[0016] For at least certain applications or batteries, there is still a need for improved separators that provide improved cycle life, reduced antimony poisoning, reduced water consumption, reduced float charge current, and / or a reduced voltage required to fully recharge the battery. More specifically, in lead-acid batteries, there is still a need for improved separators that provide improved battery life, reduced battery failure, reduced moisture loss, improved oxidation stability, improved, maintained, and / or reduced float current, improved end-of-charge ("EOC") current, reduced current and / or voltage required to charge and / or fully charge a battery, such as a deep-cycle battery, minimizes the increase in internal electrical resistance, reduces electrical resistance, increases wetting, reduces electrolyte wet-out time, reduces battery formation time, reduces acid layering, improves acid diffusion, and / or improves uniformity, as well as improved batteries containing improved separators (e.g., those operating in a partially charged state and / or deep-cycle batteries). [Means for solving the problem]

[0017] According to at least selected embodiments, the present disclosure or invention may address the above-mentioned problems or issues relating to EFB batteries and separators, and / or novel or improved separators, battery separators, membranes, separator membranes, and enhanced liquid battery separators. The present disclosure may provide, and / or may cover, a separator, a fibrous mat, a battery, a cell, and / or a method for manufacturing and / or using such a separator, a battery separator, a fibrous mat, an enhanced liquid battery separator, a cell, and / or a battery. According to at least certain embodiments, the present disclosure or invention covers a novel or improved enhanced liquid lead-acid battery separator, a fibrous mat, a liquid battery for deep-cycle applications, and / or an enhanced liquid battery, and / or a system, vehicle, etc., including such a separator, mat, or battery, and / or an improved method for manufacturing and / or using such improved separator, mat, cell, battery, system, vehicle, etc. According to at least certain embodiments, the present disclosure or invention covers an improved separator for an enhanced liquid battery, and / or an improved method for manufacturing and / or using such a battery having such an improved separator. According to at least selected embodiments, the present disclosure or invention relates to separators, in particular separators for enhanced liquid-electrolyte batteries having reduced electrical resistance and / or increased cold cranking amplifier. Also disclosed herein are methods, systems and battery separators for improving active material retention, improving battery life, reducing moisture loss, reducing internal resistance, increasing wetting, reducing acid layering, improving acid diffusion, improving cold cranking amplifier, and improving uniformity, at least in enhanced liquid-electrolyte batteries. According to at least specific embodiments, the present disclosure or invention relates to an improved separator for an enhanced liquid-electrolyte battery, comprising one or more performance-enhancing additives or coatings, optimized porosity, optimized porosity, amorphous silica, highly oil-absorbing silica, highly silanol-group silica, retention of active material in electrodes and / or improved retention, and / or any combination thereof.

[0018] According to at least selected embodiments, the Disclosure or Invention relates to lead-acid batteries, particularly liquid lead-acid batteries, and separators for various lead-acid batteries, such as liquid lead-acid batteries or enhanced liquid lead-acid batteries, having the above. According to at least selected embodiments, the Disclosure or Invention relates to novel or improved separators, cells, batteries, and / or methods for manufacturing and / or using such separators, cells, and / or batteries. According to at least certain specific embodiments, the Disclosure or Invention relates to improved separators for lead-acid batteries, and / or improved methods for using such batteries having such improved separators. Furthermore, methods, systems, and battery separators for improving active material retention, battery life, battery failure, moisture loss, oxidation stability, float current, maintenance, and / or reduction, end-of-charge (EOC) current, the current and / or voltage required to charge and / or fully charge a deep-cycle battery are disclosed herein.According to at least certain embodiments, the disclosed separator is useful in deep-cycle applications, for example, in prime movers or vehicles, and / or stationary machinery or vehicles, such as golf carts, fork trucks, inverters, renewable energy systems and / or alternative energy systems, as just a few examples, in photovoltaic and wind power systems; in particular, the disclosed separator is useful in battery systems where deep-cycle and / or partial-charge operation is part of the battery life, and more specifically, in battery systems where additives and / or alloys (e.g., antimony (Sb)) are added to the battery to improve the battery life and / or performance, and / or the battery's ability to operate in deep-cycle and / or partial-charge states.

[0019] According to at least selected embodiments, the Disclosure covers improved lead-acid batteries, such as liquid lead-acid batteries, lead-acid batteries, and / or improved systems including battery separators, improved battery separators, improved vehicles including such systems, methods of manufacture or use, or combinations thereof. According to at least certain embodiments, the Disclosure or Invention covers novel or improved liquid lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacture, testing, and use of such improved liquid lead-acid batteries, and / or combinations thereof. Also disclosed herein are methods, systems, batteries, and / or battery separators for reducing oxidation and improving battery life and performance in liquid lead-acid batteries and in batteries operating in a partially charged state.

[0020] Separators made from polyolefins, such as polyethylene, typically contain silica to facilitate wetting of the separator by hydrophilic electrolytes. In some cases, a hydrophilic material, such as a fibrous mat, is provided adjacent to the separator to assist wetting and to hold the active material coated on the positive electrode. Similarly, a fibrous mat may be provided to hold the active material coated on the negative electrode.

[0021] This application also covers new and improved lead-acid batteries, as well as vehicles having these new and improved lead-acid batteries. Liquid lead-acid batteries exhibit reduced acid formation, which, even if sufficiently tight, can result in battery inoperability. In addition to exhibiting reduced acid formation, the liquid lead-acid batteries described herein may exhibit other desirable characteristics, such as improved charge tolerance.

[0022] In one embodiment, a liquid lead-acid battery has an electrode array comprising one or more negative electrodes or plates and one or more positive electrodes or plates arranged alternately and interspersed with respect to one another, as described. In this electrode array, at least one negative electrode is wrapped with at least one of woven and nonwoven materials. Ribbed or non-ribbed porous membranes are wrapped around adjacent positive electrodes (at least one wrapped negative electrode and the positive electrode adjacent to it). In some embodiments in which the negative electrode is wrapped with a woven material, the woven material may be at least one selected from the group consisting of extrudeable mesh, woven glass mat, and carbon fiber woven material.

[0023] In other embodiments where the negative electrode is wrapped with a nonwoven material, the nonwoven material may be formed from at least one material selected from the group consisting of glass, pulp, polymer, and combinations thereof. In embodiments where the nonwoven is formed from a polymer, the nonwoven may be formed from the polymer alone or in combination with glass and / or pulp. The polymer may be at least one selected from the group consisting of polyolefins, polyesters, polyamides, polyimides, and combinations thereof. In some embodiments, the nonwoven material may comprise an inorganic powder in addition to at least one of glass, pulp, polymer, and combinations thereof. The inorganic powder may be silica. In some embodiments, the nonwoven material may be a spun-bonded-melt-woven composite material. In some embodiments, the nonwoven material is a carbon fiber nonwoven material.

[0024] The porous membrane may be ribbed in some embodiments. The porous membrane may be ribbed on one or both sides of the membrane. The ribs have a height of about 10 to about 200 μm. In some embodiments, the porous membrane may not be ribbed. Whether the porous membrane is ribbed or not, the porous membrane may be made from polyolefin, phenolic resin, polyvinyl chloride (PVC), rubber, synthetic wood pulp, glass fiber, cellulose fiber. It may be made from at least one natural or synthetic material selected from the group consisting of fibers or combinations thereof.

[0025] In some embodiments, the porous membrane may comprise polyethylene, silica, and residual or unextracted processing oil.

[0026] In some embodiments, the porous membrane around which the positive electrode is wrapped is sealed on one or more sides, two or more sides, or three sides, but not four sides. In some embodiments, the fibrous mat around which the negative electrode is wrapped is sealed on one or more sides, two or more sides, or three or more sides, but not four sides.

[0027] In another embodiment, a liquid lead-acid battery is described having an electrode array comprising one or more negative electrodes and one or more positive electrodes arranged alternately with respect to each other. In this array, a fibrous mat is at least partially integrated with the negative electrodes. In addition, in this embodiment, a ribbed or non-ribbed porous membrane is wound around either the negative electrode to which the fibrous mat is at least partially integrated, or around an adjacent positive electrode. In some embodiments, 2% to 50% of the fibrous mat is integrated with the negative electrode. In some embodiments, 5 to 25% of the fibrous mat is integrated with the negative electrode. In some embodiments, 5 to 20% of the fibrous mat is integrated with the negative electrode. In some embodiments, 10 to 15% of the fibrous mat is integrated with the negative electrode.

[0028] In some embodiments, the woven material is at least partially integrated with the negative electrode. The woven material may be at least one selected from the group consisting of extrudeable mesh, woven glass mat, and carbon fiber woven material.

[0029] In some embodiments, the nonwoven material is at least partially integrated with the negative electrode. The nonwoven material may be formed from at least one material selected from the group consisting of glass, pulp, polymer, and combinations thereof. In embodiments where the nonwoven material is formed from a polymer, the polymer may be used alone or in combination with at least glass and / or pulp. The polymer may be at least one selected from the group consisting of polyolefins, polyesters, polyamides, polyimides, and combinations thereof, or these may be used in combination. In some embodiments, the nonwoven material may comprise an inorganic powder in addition to at least one material selected from the group consisting of glass, pulp, polymer, and combinations thereof. The inorganic powder may be silica. In some embodiments, the nonwoven material may be a spun-bonded-melt-woven composite material. In some embodiments, the nonwoven material may be a carbon fiber nonwoven material.

[0030] In some embodiments, the porous membrane may be ribbed. The porous membrane may be ribbed on one or both sides of the membrane. The ribs have a height of about 10 to about 200 μm. In some embodiments, the porous membrane may not be ribbed. Whether the porous membrane is ribbed or not, the porous membrane may be made from at least one natural or synthetic material selected from the group consisting of polyolefins, phenolic resins, polyvinyl chloride (PVC), rubber, synthetic wood pulp, glass fibers, cellulose fibers, or combinations thereof. In some embodiments, the porous membrane has polyethylene, silica, and residual or unextracted processed oil.

[0031] In some embodiments, a porous membrane, in which a fibrous mat is at least partially integrated, is wrapped around either a negative electrode or an adjacent positive electrode, and is sealed on one or more sides, two or more sides, or three sides, but not four sides.

[0032] In another embodiment, a liquid lead-acid battery is described having an electrode array having one or more negative electrodes and one or more positive electrodes arranged alternately with respect to each other. In some embodiments, the negative electrodes of the electrode array are wrapped around a porous membrane having ribs on at least one side thereof, and a fibrous mat is located between the wrapped negative electrodes and the porous membrane around which the negative electrodes are wrapped. In some preferred embodiments, the ribs of the porous membrane are located at least on the side of the porous membrane closest to the fibrous mat. Whether the ribs of the porous membrane are located on the side of the porous membrane closest to the fibrous mat or on the opposite side, they may have a height of 5 μm to 300 μm or 25 μm to 200 μm.

[0033] In some embodiments, in addition to being wrapped by a porous membrane, the wrapped negative electrode is also wrapped by a fibrous mat. In some embodiments, a nonwoven or woven material is at least partially integrated with the wrapped negative electrode. In some embodiments, the nonwoven or woven material is located between the ribs of the porous membrane. In embodiments where the nonwoven or woven material is located between the ribs of the porous membrane, the nonwoven or woven material has a thickness of 50% to 150% of the height of the ribs.

[0034] In some embodiments, the woven material is located between the wound negative electrode and the porous membrane around which the electrode is wound. In such embodiments, the woven material is at least one selected from the group consisting of extrudeable mesh, woven glass mat, and carbon fiber woven material.

[0035] In some embodiments, the nonwoven material is located between the wound negative electrode and the porous membrane around which the electrode is wound. In some cases, the nonwoven material is formed from at least one material selected from the group consisting of glass, pulp, polymer, and combinations thereof. In embodiments in which the polymer is present in the nonwoven material either alone, in combination with glass and / or pulp, or in combination with another material, the polymer is at least one selected from the group consisting of polyolefin, polyester, polyamide, polyimide, and combinations thereof. In some embodiments, in addition to having at least one of glass, pulp, polymer, and combinations thereof, the nonwoven material may also have an inorganic powder. The inorganic powder may be silica. In some embodiments, the nonwoven material may be a spun-bonded-melt-woven composite material. In some embodiments, the nonwoven material is a carbon fiber nonwoven material.

[0036] The porous membrane may have ribs on both sides in some embodiments described herein. The porous membrane may be made from at least one natural or synthetic material selected from the group consisting of polyolefins, phenolic resins, polyvinyl chloride (PVC), rubber, synthetic wood pulp, glass fibers, cellulose fibers, or combinations thereof. In some embodiments, the porous membrane has polyethylene, silica, and residual or unextracted processed oil. The porous membrane wrapped around the negative electrode may be sealed in some embodiments on one or more, two or more, or three but not four sides.

[0037] In some embodiments, the fibrous mat wrapped around the negative electrode may be sealed on one or more, two or more, or three but not four sides.

[0038] In another embodiment, vehicles including a start / stop vehicle having one or more liquid lead-acid batteries are described herein.

[0039] In the first exemplary embodiment, the lead-acid battery has one or more negative electrodes, and the one or more negative electrodes The electrode array comprises one or more positive electrodes arranged alternately between them. At least one of the one or more negative electrodes is enveloped by a fibrous mat, and one or more positive electrodes adjacent to at least one of the one or more negative electrodes are enveloped by a porous membrane. The porous membrane may be a microporous battery separator.

[0040] In exemplary embodiments, the fibrous mat may be a nonwoven fabric, mesh, fleece, and / or a combination thereof. The fibrous mat may further be glass fiber, pulp, polymer, and / or a combination thereof. The fibrous mat may also be formed from a polymer, and in addition, from glass fiber, pulp, and / or a combination thereof, and the polymer may be polyolefin, polyester, polyamide, polyimide, and / or a combination thereof. The fibrous mat may be an inorganic material, such as silica. The fibrous mat may be a spun-bonded-melt-nonwoven composite material or a carbon fiber nonwoven material, and the like.

[0041] An exemplary porous membrane may comprise one or more arrays of ribs on at least one of its surfaces, or one or more arrays of ribs on two of its surfaces. The ribs may have a height of about 10 μm to about 2.0 mm. The porous membrane may be one or more of the following: natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and / or combinations thereof. Alternatively, the porous membrane may be polyethylene, silica, and processing oil, where the processing oil is present in an amount of about 5% to about 15% by weight of the porous membrane.

[0042] In a particular selected embodiment, the porous membrane has a porosity of approximately 55%, approximately 60%, or more than approximately 65%.

[0043] In another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be enveloped around the positive electrode and sealed on one side, two sides, and / or three sides of the positive electrode.

[0044] In another exemplary embodiment, the fibrous mat of the exemplary lead-acid battery may be enveloped around the negative electrode and sealed on one, two, and / or three sides of the negative electrode.

[0045] In another exemplary embodiment, a preferred lead-acid battery may include an electrode array comprising one or more negative electrodes and one or more positive electrodes arranged alternately between the one or more negative electrodes. The battery may further include a fibrous mat assembly comprising one or more electrodes and a fibrous mat at least partially integrated with at least one of the negative electrodes. The porous membrane may be a microporous membrane and may envelope one or more of the one or more electrodes and the fibrous mat assembly, or at least one of the one or more positive electrodes adjacent to the one or more electrodes and the fibrous mat assembly. In exemplary embodiments, the fibrous mat may be integrated with the active material to about 2% to about 50%, about 5% to about 25%, about 5% to about 20%, or about 10% to about 15% of the mat thickness of the fibrous mat.

[0046] Any exemplary fibrous mat may be one or more of nonwoven fabrics, meshes, fleeces, and / or combinations thereof. Furthermore, the fibrous mat may be one or more of glass fibers, pulps, polymers, and / or combinations thereof. In addition, the fibrous mat may be formed from polymers, and also from one or more of glass fibers, pulps, and / or combinations thereof, wherein the polymers may be polyolefins, polyesters, polyamides, polyimides, and / or combinations thereof. It may be one or more of the following:

[0047] In another embodiment of the exemplary lead-acid battery, the exemplary fibrous mat may be an inorganic material, such as silica. The fibrous mat may be a spun-bonded melt nonwoven fabric, a carbon fiber nonwoven fabric, and the like.

[0048] In a further embodiment of the exemplary lead-acid battery, the exemplary porous membrane may have one or more arrays of ribs on one or two of its surfaces. The ribs of one or more arrays of ribs may have a height of about 10 μm to about 2.0 mm.

[0049] Exemplary porous membranes may be at least one of natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and / or combinations thereof. In one particular embodiment, the porous membrane may be polyethylene, silica, and processing oil.

[0050] In another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be enveloped around the positive electrode and sealed on one, two, and / or three sides of the positive electrode. In yet another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be sealed on one, two, and / or three sides of one or more electrodes and fibrous mat assemblies.

[0051] In a further selected embodiment of an exemplary preferred embodiment, the lead-acid battery comprises an electrode array of one or more negative electrodes and one or more positive electrodes arranged alternately with respect to one another. A porous membrane envelope is further provided, enveloping at least one of the one or more negative electrodes located therein, wherein the porous membrane includes ribs on one or more of its surfaces, and a fibrous mat is disposed within the envelope. The ribs may be at least partially on the surface of the porous membrane adjacent to the fibrous mat. The ribs may have a height of about 10 μm to about 2.0 mm, or about 5 μm to about 300 μm, or about 25 μm to about 200 μm. The fibrous mat may also envelop at least one of the one or more negative electrodes. Furthermore, the fibrous mat may be at least partially integrated with the negative electrode.

[0052] Alternatively, the fibrous mat may be a separate piece positioned between the ribs and may have a thickness of about 50% to about 150% of the rib height. In a selected embodiment of the present invention, the fibrous mat may be positioned between the negative electrode and the porous membrane. The fibrous mat may be one or more of glass fibers, pulp, polymers, and combinations thereof. The fibrous mat may be formed from a polymer in combination with one or more of glass fibers, pulp, and combinations thereof; where the polymer may be one or more of polyolefins, polyesters, polyamides, polyimides, and combinations thereof. The fibrous mat may also be an inorganic material, such as silica. The fibrous mat may be a spun-bonded-melt-nonwoven composite material or a carbon fiber nonwoven material.

[0053] Furthermore, the fibrous mat may further contain carbon components either as part of the mat or in a layer adjacent to the negative electrode. For example, the fibrous mat may contain carbon fibers, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, Ketjenblack, carbon fibers, carbon filaments, carbon nanotubes, open-cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (Bucky Balls), aqueous carbon suspension, scaly graphite, carbon oxide, and combinations thereof. The fibrous mat may also contain nucleating additives, such as the above-mentioned carbon, or barium sulfate ( It may contain BaSO4.

[0054] In a selected embodiment, the porous membrane may have ribs on two of its surfaces. The porous membrane may also be one or more of the following: natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and combinations thereof. Specifically, the porous membrane may be polyethylene, silica, and processing oil.

[0055] In a selected embodiment of the present invention, the porous membrane may be sealed on one side of the negative electrode, two sides of the negative electrode, or three sides of the negative electrode. Alternatively, the fibrous mat may be sealed on one side of the negative electrode, two sides of the negative electrode, and three sides of the negative electrode.

[0056] In a selected embodiment of the present invention, the system comprises a vehicle utilizing one or more batteries substantially described herein. The vehicle may be an automobile, truck, motorcycle, all-terrain vehicle, forklift, golf cart, hybrid vehicle, hybrid electric vehicle, electric vehicle, idle-start-stop ("ISS") vehicle, electric rickshaw battery, electric tricycle, electric bicycle, wheelchair, or ship.

[0057] In selected embodiments, the lead-acid batteries substantially described herein may be plate batteries, liquid lead-acid batteries, reinforced liquid lead-acid batteries ("EFB"), valve-regulated lead-acid ("VRLA") batteries, gel batteries, absorbent glass mat ("AGM") batteries, deep-cycle batteries, tubular batteries, inverter batteries, vehicle batteries, start-light-ignition ("SLI") vehicle batteries, idle-start-stop ("ISS") vehicle batteries, automobile batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, wheelchair batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, or marine batteries.

[0058] In an optional embodiment, the method is provided for preventing or mitigating acid displacement in a lead-acid battery, liquid lead-acid battery, or liquid lead-acid battery that is operated in or intended to be operated in a partially charged state. The method may include manufacturing a battery having substantially the same structure as any of the batteries described herein.

[0059] Novel or improved systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, electrodes, and / or methods for manufacturing and / or using such batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, fibrous mats, cells, and / or electrodes as shown or described herein.

[0060] Novel or improved batteries, in particular lead-acid batteries described and / or indicated herein; novel or improved systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, electrodes, and / or methods for manufacturing and / or using such systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, and / or electrodes; improved batteries having improved lead-acid battery separators, and / or improved methods for using such batteries having such improved separators; in lead-acid batteries, improving battery life, reducing battery failure, reducing moisture loss, reducing float current, reducing increase in internal resistance, increasing wettability, reducing acid layering, improving acid diffusion, and active material Methods, systems, processes, and battery separators for preserving, reducing delamination of active material, and / or improving uniformity; improved lead-acid battery separators comprising an improved functional coating, improved battery separators for reducing acid layering, improved battery separators for improving acid diffusion, improved lead-acid batteries for preserving active material, improved lead-acid battery separators for reducing delamination of active material, improved lead-acid batteries comprising such improved separators, long-life automotive lead-acid batteries, improved liquid lead-acid batteries, and / or batteries having reduced acid layering, improved acid diffusion, improved active material preservation capability, and / or improved active material delamination reduction capability; batteries having a polyethylene separator and a negative electrode with a fibrous mat disposed between them, and / or methods for manufacturing and / or using such batteries; batteries having a porous membrane and a fibrous mat laminated thereon, wherein the fibrous mat is adjacent to the negative electrode in such batteries, and / or methods for manufacturing and / or using such batteries.

[0061] As described herein, exemplary separators may be used in lead-acid batteries used in a variety of applications. Such applications may include, for example: partially charged applications; deep cycle applications; automotive applications; truck applications; motorcycle applications; power applications, e.g., fork trucks, golf carts (also called golf trolleys), etc.; electric vehicle applications; hybrid electric vehicle ("HEV") applications; ISS vehicle applications; electric rickshaw applications; electric tricycle applications; electric bicycle applications; boat applications; and energy storage applications, e.g., renewable and / or alternative energy storage, e.g., wind energy, solar energy, etc. Furthermore, exemplary separators may be used in a variety of batteries. Such exemplary batteries may include, for example: liquid lead-acid batteries, e.g., enhanced liquid lead-acid batteries; AGM batteries; VRLA batteries; plate batteries; tubular batteries; partially charged batteries; deep cycle batteries; automotive batteries; truck batteries; motorcycle batteries; power batteries, e.g., fork truck batteries, golf cart batteries (also called golf carts), etc.; electric vehicle batteries; hybrid electric vehicle ("HEV") batteries; ISS vehicle batteries; electric rickshaw batteries; electric tricycle batteries; electric bicycle batteries; boat batteries; energy storage and energy integration batteries, e.g., renewable and / or alternative energy storage and energy integration and storage, e.g., wind energy, solar energy, etc. [Brief explanation of the drawing]

[0062] [Figure 1] Figure 1 schematically shows a typical liquid lead-acid battery. [Figure 2A] Figure 2A is a side view showing an embodiment of an electrode / separator array according to an exemplary embodiment of this specification. [Figure 2B] Figure 2B is a side view showing an embodiment of an electrode / separator array according to an exemplary embodiment of this specification. [Figure 3A] Figure 3A is a side view showing an embodiment of an electrode / separator array according to an exemplary embodiment of this specification. [Figure 3B]Figure 3B is a side view showing an embodiment of an electrode / separator array according to an exemplary embodiment of this specification. [Figure 4] Figure 4 is a side view of an embodiment of an electrode / separator array according to one exemplary embodiment of this specification. [Figure 5A] Figure 5A is a side view showing an embodiment of an electrode / separator array according to one exemplary embodiment of this specification. [Figure 5B] Figure 5B is a side view showing an embodiment of an electrode / separator array according to one exemplary embodiment of this specification. [Figure 6A] Figure 6A is a side view showing an embodiment of an electrode / separator array according to one exemplary embodiment of this specification. [Figure 6B] Figure 6B is a side view showing an embodiment of an electrode / separator array according to one exemplary embodiment of this specification. [Figure 7A] Figure 7A is a photograph of an exemplary fibrous mat described in this disclosure. [Figure 7B] Figure 7B is a photograph of an exemplary fibrous mat described in this disclosure. [Figure 8A] Figure 8A is a higher-resolution photograph of the exemplary fibrous mat shown in Figure 7A, taken from above. [Figure 8B] Figure 8B is a higher-resolution photograph of the exemplary fibrous mat shown in Figure 7B, taken at an oblique angle to the mat lying on its side. [Figure 9] Figure 9 shows low-magnification SEM images comparing an exemplary fibrous mat described herein with a conventional glass mat. [Figure 10] Figure 10 shows a higher magnification SEM image of an exemplary fibrous mat described in this disclosure than that shown in Figure 11. [Figure 11] Figure 11 is an SEM image of an exemplary fibrous mat described herein, with fiber diameters highlighted. [Figure 12]Figure 12 is a SEM image of an exemplary fibrous mat described herein, with the pore regions highlighted. [Figure 13A] Figure 13A shows the longitudinal ribs in the vertical direction. [Figure 13B] Figure 13B shows horizontal or transverse ribs in the width direction. [Figure 14A] Figure 14A is an exemplary side view of a porous membrane illustrating the dimensions of the positive electrode rib and negative electrode rib membranes. [Figure 14B] Figure 14B is an exemplary side view of a porous membrane illustrating the dimensions of the positive and negative electrode ribs. [Figure 15A] Figure 15A is an exemplary side view of a porous membrane illustrating the dimensions of the positive and negative electrode ribs. [Figure 15B] Figure 15B is an exemplary side view of a porous membrane illustrating the dimensions of the positive and negative electrode ribs. [Modes for carrying out the invention]

[0063] The embodiments described herein can be best understood by referring to the following detailed description, examples, and drawings or figures (i.e., "Fig. (FIG.)" or "Figs. (Figs.)"). In particular, various batteries, vehicles, or devices, and methods for preventing oxidation are described herein, but are not limited to the specific embodiments presented in the detailed description, examples, and figures. It is recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the subject matter disclosed.

[0064] lead acid battery Referring here to Figure 1, an exemplary liquid lead-acid battery 50, e.g., EFB, comprises an array 50a of alternating positive electrodes 52 and negative electrodes 54, such that the positive electrodes 52 are alternately arranged between the negative electrodes 54. The array 50a further comprises a separator assembly 100 alternately arranged between each electrode 52, 54, such that the separator assembly 100 prevents contact between the electrodes 52, 54. The array 50a is substantially immersed in a sulfuric acid (H2SO4) electrolyte 56 (for example, sulfuric acid having an exemplary specific gravity between approximately 1.20 and 1.35 relative to water). The positive electrode 52 is electrically in communication with a positive terminal 51, and the negative electrode 54 is electrically in communication with a negative terminal 53. The separator assembly 100 includes a porous membrane (200 in Figure 2A-8) and may additionally include one or more fibrous mats (300 in Figure 2A-8).

[0065] The lead-acid batteries described herein are not limited and may include liquid lead-acid batteries, such as enhanced liquid lead-acid batteries, absorbent glass mat ("AGM") batteries, valve-regulated lead-acid ("VRLA") batteries, gel batteries, and the like. In some preferred embodiments, the following applies: The lead-acid batteries described herein are, at the very least, liquid lead-acid batteries, since the disclosure herein is intended to address the problems of liquid lead-acid batteries that operate in or are in a partially charged state, namely acidification and active material shedding.

[0066] As described herein, exemplary separators may be used in lead-acid batteries used in a variety of applications. Such applications may include, for example: partially charged applications; deep cycle applications; automotive applications; truck applications; motorcycle applications; power applications, e.g., fork trucks, golf carts (also called golf trolleys), etc.; electric vehicle applications; hybrid electric vehicle ("HEV") applications; ISS vehicle applications; electric rickshaw applications; electric tricycle applications; electric bicycle applications; boat applications; and energy storage applications, e.g., renewable and / or alternative energy storage, e.g., wind energy, solar energy, etc. Furthermore, exemplary separators may be used in a variety of batteries. Such exemplary batteries may include, for example: liquid lead-acid batteries, e.g., enhanced liquid lead-acid batteries; AGM batteries; VRLA batteries; plate batteries; tubular batteries; partially charged batteries; deep cycle batteries; automotive batteries; truck batteries; motorcycle batteries; power batteries, e.g., fork truck batteries, golf cart batteries (also called golf carts), etc.; electric vehicle batteries; hybrid electric vehicle ("HEV") batteries; ISS vehicle batteries; electric rickshaw batteries; electric tricycle batteries; electric bicycle batteries; boat batteries; energy storage and energy integration batteries, e.g., renewable and / or alternative energy storage and energy integration and storage, e.g., wind energy, solar energy, etc.

[0067] Negative and positive electrodes The positive and negative electrodes or positive and negative electrode plates disclosed herein are not limited and may be any positive or negative electrodes known to be acceptable for use in lead-acid batteries. Typically, in a lead-acid battery, the negative electrode or plate is provided as a lead oxide (PbO2) grid having a negative electrode active material ("NAM") coating the negative electrode grid, and the positive electrode or plate is provided as a sponge lead (Pb) grid having a positive electrode active material ("PAM") coating the positive electrode grid. When used herein, "electrodes" and "plates" may be used interchangeably. In some preferred embodiments, the electrodes may have a plant plate structure, a flat plate structure, or a tubular electrode structure.

[0068] An exemplary electrode having a flat plate structure comprises a grid and an active material (e.g., a positive electrode active material ("PAM") or a negative electrode active material ("NAM")). The grid may consist of lead alone, or a lead alloy having at least one of antimony, calcium, tin, selenium, and combinations thereof. The amount of additives to the lead may be, for example, about 1% to about 20%, about 1% to about 15%, about 1% to about 10%, about 1% to about 6%, about 1% to about 5%, about 1% to about 4%, about 1% to about 3%, about 1% to about 2%, etc. In a particular selected embodiment, the grid may consist of a lead-antimony alloy. Antimony is said to improve hardness. In another selected embodiment, the grid may consist of a lead-calcium alloy. Calcium is said to improve hardness. In some selected embodiments, tin may be added to the lead-calcium or lead-antimony alloy to improve cyclability. In electrodes having a flat plate structure, the active material is formed by applying a paste onto a grid. The paste may comprise a mixture of lead (e.g., lead oxide), water, and sulfuric acid. After the application process, in some embodiments, the electrodes may be cured.

[0069] An exemplary electrode having a tubular structure comprises a series of spines, called a comb, extending downward from a top rod. The comb may consist of lead alone, or lead and at least one selected from antimony, calcium, tin, and selenium. Additives to lead The amount may be 1%-20%, 1%-15%, 1%-10%, 1%-6%, 1%-5%, 1%-4%, 1%-3%, 1%-2%, etc. In some preferred embodiments, the comb or grid may consist of lead and antimony. Antimony is said to improve hardness. In some other preferred embodiments, the grid consists of lead and calcium. Calcium is said to improve hardness. In some embodiments, tin may be added to the lead and calcium or lead and antimony alloy to improve cyclability. Parallel tubes or gauntlets surround the spine and hold the active material (positive or negative). These gauntlets may consist of porous inert fabric or nonwoven fabric.

[0070] electrode array Referring here to Figures 2A and 2B, an exemplary electrode / separator array 50a comprises an array of positive electrodes 52, accompanied by an array of negative electrodes 54 arranged alternately between them, as generally described above, and an array of separator assemblies 100 arranged alternately between each electrode 52, 54. As shown, the separator assembly 100 comprises a porous membrane 200 which may or may not have positive electrode ribs (not shown in Figure 2A or 2B, but described below) and / or negative electrode ribs (not shown in Figure 2A or 2B, but described below), and a fibrous mat 300. Alternatively, the fibrous mat 300 may be one or more mats. As shown in Figure 2A, the fibrous mat 300 is positioned adjacent to the positive electrode(s) 52 and the porous membrane 200; the porous membrane 200 is positioned adjacent to the negative electrode(s) 54 and the fibrous mat 300. As shown in Figure 2B, the fibrous mat 300 is positioned adjacent to and in close contact with the negative electrode(s) 54 and the porous membrane 200; the porous membrane 200 is positioned adjacent to the positive electrode(s) 52 and the fibrous mat 300. The separator assembly 100 may provide porous membranes 200 and fibrous mat 300 bonded to each other via adhesive, heat scribing, ultrasonic welding or sealing, ultrasonic sawing, co-extrusion, and / or a combination thereof. Alternatively, the separator assembly 100 may provide porous membranes 200 and fibrous mat 300 that are not bonded to each other. As shown, the separator assembly 100 is provided in a loose-leaf configuration. Alternatively, the separator assembly 100 may be provided as an envelope, hybrid envelope, pocket, sleeve, wrap, fold, or a combination thereof. The combination refers to the possibility that different configurations may be used throughout the electrode / separator array 50a.

[0071] Referring here to Figures 3A and 3B, an exemplary electrode / separator array 50a comprises an array of positive electrodes 52, accompanied by an array of negative electrodes 54 arranged alternately between them, as generally described above, and an array of separator assemblies 100 arranged alternately between each electrode 52, 54. As shown, the separator assembly 100 comprises a porous membrane 200 which may or may not have positive electrode ribs (not shown in Figure 3A or 3B for clarity, but described below) and / or negative electrode ribs (not shown in Figure 3A or 3B for clarity, but described below), and a fibrous mat 300. Alternatively, the fibrous mat 300 may be one or more mats. As shown in Figure 3A, the fibrous mat 300 is arranged in an envelope form around the positive electrode(s) 52; the porous membrane 200 is arranged in an envelope form around the fibrous mat 300. As shown in Figure 3B, the fibrous mat 300 is arranged in close contact with the negative electrode(s) 54 in an envelope form; the porous membrane 200 is arranged around the fibrous mat 300 in an envelope form. The separator assembly 100 may provide porous membranes 200 and fibrous mats 300 that are attached to each other by adhesive, heat scribing, ultrasonic welding or sealing, ultrasonic sawing, co-extrusion, and / or a combination thereof. Alternatively, the separator assembly 100 may provide porous membranes 200 and fibrous mats 300 that are not attached to each other. As shown, the separator assembly 100 is envelope It is provided in an envelope configuration. Alternatively, the separator assembly 100 may be provided as a hybrid envelope, pocket, sleeve, wrap, fold, or a combination thereof. The combination refers to the possibility that different configurations may be used throughout the electrode / separator array 50a.

[0072] Referring here to Figure 4, an exemplary electrode / separator array 50a comprises an alternating array of positive electrodes 52 and negative electrodes, as generally described above. In Figure 4, the separator assembly 100 comprises a porous membrane 200 which may or may not have positive electrode ribs (not shown in Figure 4, but described below) and / or negative electrode ribs (not shown in Figure 4, but described below), and a fibrous mat 300. Alternatively, the fibrous mat 300 may be one or more mats. As shown, the fibrous mat 300 is arranged around the negative electrode(s) 52 in an envelope or pocket form. The porous membrane 200 is arranged around the positive electrode(s) 54 in an envelope or pocket form. The porous membrane and the fibrous mat may be configured as a separator envelope which may or may not be a hybrid envelope configuration. Alternatively, the non-adhered porous membrane 200 and fibrous mat 300 may be provided as loose-leaf, pocket, sleeve, wrap, fold, S-wrap, Z-fold, or a combination thereof. The combination refers to the possibility that different configurations may be used throughout the electrode / separator array 50a.

[0073] Referring here to Figures 5A and 5B, an exemplary embodiment comprises a fibrous mat(s) 300 at least partially integrated with the negative electrode 54 active material of the array 50a. In Figure 5A, the porous membrane 200 is arranged in an envelope form around the negative electrode 54 and the fibrous mat(s) 300 as a whole. In Figure 5B, on the other hand, the porous membrane is arranged in an envelope form around the positive electrode 52. With respect to the porous membrane 200, it may be provided as an envelope (not shown), and may be a hybrid envelope, loose leaf, pocket, sleeve, wrap, etc., or a combination thereof. The combination refers to the possibility that different configurations may be used throughout the electrode / separator array 50a. The porous membrane 200 may or may not have positive electrode ribs (not shown in Figure 5A or 5B for clarity, but described below) and / or negative electrode ribs (not shown in Figure 5A or 5B for clarity, but described below).

[0074] As described above, the fibrous mat 300 is at least partially integrated with the negative electrode active material. Therefore, the fibrous mat is not only in contact with the surface of the negative electrode, but is also integrally attached to the negative electrode. The negative electrode active material enters the gaps and pores of the fibrous mat so as to form a layer 350 which is a mixture of the fibrous mat 300 and the negative electrode active material ("NAM") of the negative electrode 54. In some embodiments, 2% to 50% of the fibrous mat is integrated with the NAM. This means that 2% to 50% of the thickness of the fibrous mat is embedded in the NAM, forming a composite layer 350 which is a mixture of the fibrous mat 300 and the NAM. In some embodiments, 5% to 25% of the fibrous mat 300 is integrated with the negative electrode 54. In some embodiments, 5% to 20% of the fibrous mat 300 is integrated with the negative electrode 54. In some embodiments, 10% to 15% of the fibrous mat 300 is integrated with the negative electrode 54.

[0075] Referring here to Figures 6A and 6B, an exemplary electrode / separator array 50a comprises an array of positive electrodes 52, an array of negative electrodes 54 arranged alternately between them, and an array of separator assemblies 100 arranged alternately between each electrode 52, 54, as generally described above. In Figure 6, the separator assembly 100 comprises positive electrode ribs (not shown in Figure 6 for clarity, but described below) and / or negative electrode ribs (not shown in Figure 6 for clarity, but described below). The separator assembly comprises a porous membrane 200, which may or may not be present, and a fibrous mat 300. As shown, the fibrous mat 300 is positioned adjacent to the positive electrode(s) 52 and the porous membrane 200, and the porous membrane 200 is positioned adjacent to the negative electrode(s) 54 and the fibrous mat 300. The separator assembly 100 may provide porous membranes 200 and fibrous mats 300 that are attached to each other by adhesive, heat scribing, ultrasonic welding or sealing, ultrasonic sawing, co-extrusion, and / or a combination thereof. Alternatively, the separator assembly 100 may provide porous membranes 200 and fibrous mats 300 that are not attached to each other. As shown in Figures 6A and 6B, an exemplary separator assembly 100 may comprise a porous membrane 200 having negative electrode ribs 206 (i.e., ribs on the porous membrane surface facing the negative electrode) arranged longitudinally on the porous membrane 200 (i.e., arranged longitudinally from the top to the bottom of the battery). As shown in Figure 6A, exemplary strips of fibrous mat 300 are positioned between these negative electrode ribs 206. The strips of fibrous mat 300 may have a thickness of approximately 50% to approximately 150% of the rib height 206. As shown in Figure 6B, exemplary porous mat 300 is positioned between the porous membrane 200 and the negative electrode 54.

[0076] It is recognized that fibrous mats prevent or delay the process of detachment or separation of the active material from adjacent electrodes, regardless of whether the active material is NAM or PAM.

[0077] fibrous mat Preferred fibrous mat compositions may be, for example, glass fibers, synthetic fibers, or any combination thereof. An exemplary embodiment of the fibrous mat may consist of 5% to 25% synthetic fibers, with the remainder being glass and / or a binder. However, the mat may be entirely glass or entirely synthetic. Such examples of synthetic fibers may be polyolefins, polyethylene, polypropylene, polyester, polyethylene terephthalate ("PET"), polyamides, polyimides, acrylics, other plastics, pulp; and combinations thereof. Furthermore, the fibrous composition may be a mixture of fibers having polymers, homopolymers, or copolymers, or combinations thereof. All fibrous mat compositions are preferably resistant to the acidic electrolytes of lead-acid batteries. These materials tend to be hydrophobic, thus causing gas trapping. Therefore, surfactant coatings generally described herein may be added.

[0078] The fibrous mat may further comprise a filler, such as particulate silica, which increases the surface area and reduces the pore size. Other exemplary fillers may include silica, talc (Mg2SiO4), aluminum oxide, alumina hydrate, titanium oxide, zirconium oxide, sodium silicate, and combinations thereof. Such fillers and silica may also be used in porous membranes, which are further described herein. The fibrous mat composition may further comprise soluble fibers. The fibrous mat may also comprise a gelling agent that helps resist acid formation. The fibrous mat may also comprise wetting agent additives or coatings, which are generally described below. An exemplary fibrous mat may further comprise at least one of carbon, such as graphite, acetylene black, and graphene.

[0079] An exemplary fibrous mat may consist of randomly located fibers, cords, filaments, or fine wires held together by mechanical bonding, by melting the fibers, and / or by binding the fibers to a binder, such as an adhesive. Web formation can be achieved by various processes including dry placement, wet placement, wet felting, needle felting, carrotting, or extrusion of filaments onto a moving belt. Within the extrusion category, two processes include spunbonding, e.g., producing spunbond nonwovens, and meltblowning, e.g., producing meltblown nonwovens. See urbak, A., Ed., Nonwovens: Theory, Process, Performance, and Testing, TAPPI Press, Atlanta, Ga. (1993). Chapter 8 is incorporated herein by reference. Spunbond nonwovens are formed by extruded, stretched, and then arranged on a continuous belt. Meltblown nonwovens are formed by extruding a molten polymer through a mold, diluting the extruded filaments with air or steam, and collecting them on a moving belt. Nonwoven materials may also be meltblown-spunbond materials having one or more meltblown layers and one or more spunbond layers provided in any order. For example, spunbond layers and meltblown layers in any order, or two or more layers.

[0080] The fibrous mats described herein are not limited. The mats may be nonwoven materials, mesh, fleece, felt, scrim, pasting paper, or combinations thereof. For example, a fibrous mat may be a composite material of adjacent nonwoven and mesh materials, multiple adjacent nonwoven mats of different materials, multiple adjacent piles of the same nonwoven material, or various other combinations. The composite material may have one, two, or more (three or more) piles or layers of materials adjacent to or optionally adhering to each other.

[0081] Referring here to Figures 7A and 7B, photographs of exemplary embodiments of the fibrous mat are shown. Figures 8A and 8B are higher resolution photographs of exemplary embodiments of the fibrous mat. The fibrous mat may be a nonwoven fabric, fleece, felt, mesh, or any combination of these layers. The fibrous mat may be a single-layer, double-layer, or other multi-layer mat. The exemplary nonwoven mat may have a thickness in the range of approximately 100 μm to approximately 900 μm, preferably in the range of approximately 200 μm to approximately 450 μm. Figures 8A and 8B show a bundled fiber pattern, which can be achieved during mat formation, and as the fiber carrier fluid flows out, the fibers may aggregate at certain low points in the outflowing mesh. The mat may also contain combed fibers.

[0082] Exemplary fibers, filaments, or cords used in nonwoven fabrics may have a fiber thickness or diameter of approximately 7.2 μm (±0.5 μm) with a ±95% confidence limit. Table 1 below compares the fiber diameter (μm) of the nonwoven fabric according to the present invention with that of a conventional glass mat.

[0083] [Table 1]

[0084] An example of nonwoven fabric has a density of approximately 1500 l / m². 2 • s ~ approximately 2500 l / m 2 It may have a desirable air permeability in the range of s.

[0085] The exemplary nonwoven fabric may preferably have a pore diameter of approximately 4.0 μm to less than 5.0 μm (measured as an effective diameter via SEM measurement). The fibrous mat preferably has a pore diameter smaller than the particle size of the active material used in the accompanying negative or positive electrode. Table 2 below shows the pore diameter and area of ​​an exemplary fibrous mat according to the present invention compared to a conventional glass mat. Compare it to the one.

[0086] [Table 2]

[0087] The exemplary fibrous mat may have a preferred electrical resistance (“ER”) in the range of approximately 6 mΩ·cm 2 to approximately 14 mΩ·cm 2 , preferably less than 14 mΩ·cm 2 or less than 13 mΩ·cm 2 or less than 12 mΩ·cm 2 or less than 11 mΩ·cm 2 The exemplary fibrous mat may have a preferred electrical resistance (“ER”) in the range of approximately 6 mΩ·cm

[0088] The exemplary fibrous mat may have a preferred basis weight or grammage in the range of approximately 50 g / m 2 to about 100 g / m 2 and in some embodiments, in the range of 60 g / m 2 to approximately 80 g / m 2 The exemplary fibrous mat may have a preferred basis weight or grammage in the range of approximately 50 g / m

[0089] The exemplary fibrous mat may have a preferred binder content in the range of approximately 15% to approximately 21%.

[0090] The exemplary fibrous mat may have a preferred thickness in the range of approximately 200 μm to about 450 μm, and in certain embodiments, in the range of about 350 μm to approximately 450 μm.

[0091] The exemplary fibrous mat may have a preferred machine direction (MD) tensile strength of approximately 200 N / 50 mm and a preferred cross machine direction (CMD) tensile strength of approximately 150 N / 50 mm.

[0092] Furthermore, the fibers of the fibrous mat may be solid or hollow, and the cross-sectional shape of the fibers may be round, circular, oval or elliptical, kidney bean-shaped, dog bone-shaped, racetrack-shaped, polygonal, or any combination thereof. Also, the exemplary fibers may have a plurality of components in a parallel configuration, or a core-sheath configuration, or a sea-island configuration. Also, the core-sheath configuration may exhibit any of the above shapes, and the core may be centered or eccentric.

[0093] The fibrous mat may be provided throughout the electrode / separator array in sheet form, or in the form of a wrap, pocket, sleeve, envelope, or a combination thereof. An exemplary fibrous mat may envelop the negative electrode ("negative electrode envelope mat"), resulting in the separator having two inner surfaces facing the negative electrode and two opposite surfaces facing the adjacent positive electrode and / or porous membrane(s). Alternatively, another exemplary fibrous mat may envelop the positive electrode ("positive electrode envelope separator"), resulting in the fibrous mat having two inner surfaces facing the positive electrode and two opposite surfaces facing the adjacent positive electrode and / or porous membrane(s). In such an envelope mat, the bottom edge may be a folded or sealed fold edge around the bottom of the enveloped electrode. Furthermore, the horizontal edge may be an open, continuously sealed seam edge, or an intermittently sealed seam edge. The edges may be bonded or sealed by adhesive, heat, ultrasonic welding, or any combination thereof.

[0094] Certain exemplary fibrous mats of a separator assembly can be processed to form a hybrid envelope. The hybrid envelope may be provided by forming one or more slits or openings before, during, or after the envelope is formed. The length of the openings or slits may be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the total edge length. The length of the openings may be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the total edge length. The hybrid envelope may have at least 1 to 5 or more openings, 1 to 4, 2 to 4, 2 to 3, or 2 openings, which may or may not be evenly distributed along the length of the bottom edge. It is preferable that there are no openings at the corners of the envelope.

[0095] Some other exemplary embodiments of the separator assembly configuration include: a negative or positive envelope; a negative or positive sleeve; a negative or positive hybrid envelope; and both electrodes may be enveloped, sleeved, or any combination thereof.

[0096] Sealing may be carried out by at least one of the following: adhesive, heat (melt) sealing, mechanical sealing, ultrasonic sealing, compression, welding, or a combination thereof. Mechanical sealing may be performed using pressure rolls with or without gear teeth. Mechanical sealing may be performed with or without the addition of heat. Those skilled in the art will understand that certain sealing methods may be more appropriate depending on the material of the fibrous mat. For example, adhesive sealing may be more appropriate mainly for glass fiber mats, while adhesive sealing or heat sealing may be more appropriate when the fibrous mat contains a polymer to be melted.

[0097] Referring to Figure 9, four low-magnification SEM images are shown, taken from two separate locations of an exemplary fibrous mat and two separate locations of a conventional glass mat. The images show that the exemplary fibrous mat has a more densely packed fiber web than the conventional glass mat. Furthermore, the fibers and openings of the exemplary fibrous mat are smaller than those of the conventional glass mat.

[0098] In Figure 10, SEM images were obtained from each sample, from two separate locations, and then from samples taken from two separate regions. This was done to avoid bias in any of the regions. These images were taken at a higher magnification than those in Figure 9. These images further show the fiber packing density and also some bundling of fibers, possibly due to the binder used and its content. Useful fibrous mats in the various embodiments described herein may contain tufts or bundles of fibers, e.g., tufts or bundles of glass fibers and / or synthetic fibers. Such tufts or bundles may be twisted in certain embodiments before the fibers are bonded together. In such embodiments, twisting may occur, and a binder may be applied to hold such twisting in place. In such embodiments, a separator having a fibrous mat with tufts or bundles of fibers may exhibit increased strength compared to a separator having a conventional mat. Similarly, if the fibers are twisted, such a separator having such a fibrous mat may exhibit an even more significant increase in strength compared to a separator having a conventional mat. When a wet laid process is used to produce such fibrous mats according to various preferred embodiments defined herein, composite fiber bundles may be produced, such composite fiber bundles comprising glass fibers and synthetic polymer fibers, as in just one example, polyester fibers or PET fibers.

[0099] In addition, fibrous mats can be formed by bundles of fibers either before or during the formation of the mat. The bundles can be combed or twisted by multiple fibers having different material compositions, different cross-sectional shapes, different fiber diameters, and any combination thereof. The bundles may be arranged in a patterned orientation, randomly piled, or a combination thereof. The bundled fibers may be arranged on and / or in the randomly arranged nonwoven or fibrous mat layer. The resulting fibrous mat may therefore have a textured surface, a smooth surface, or a combination thereof. Figures 8A and 8B are photographs of an exemplary fibrous mat having a textured surface. The bundles may also be formed during the manufacturing of the mat. The bundles may be easily formed by carrier wires or surface profiles used in the mat manufacturing. Furthermore, the mat may be arranged in two separate processes. For example, the bundles may be formed by a water-soluble binder, and then a second layer of nonwoven fibers may be arranged below to hold the fibers together. The bundles may be piled on either or both surfaces of the mat.

[0100] Figure 11 shows an image used to measure the fiber diameter of an exemplary fibrous mat, captured by the straight-line distance across individual fibers; fibers in a bundle were not measured, and two diameters were captured for each measured fiber (where possible). The data from Figure 12 is shown in Table 1 above. Figure 12 is an image used to measure the pore diameter of a fibrous mat. The data from Figure 12 is shown in Table 2 above.

[0101] The fibrous mat may further contain carbon components either as part of the mat or in a layer adjacent to the negative electrode. For example, the fibrous mat may contain carbon fibers, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, Ketjenblack, carbon fibers, carbon filaments, carbon nanotubes, open-cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (Bucky Balls), aqueous carbon suspension, scaly graphite, carbon oxide, and combinations thereof. The fibrous mat may also contain nucleating additives, such as the above-mentioned carbon or barium sulfate (BaSO4).

[0102] porous membrane physical properties The porous membrane is not particularly limited and may be any porous membrane; a porous membrane having pores of any size (e.g., macroporous, microporous, nanoporous, etc.) and made of any material; in some preferred embodiments, the porous membrane is a microporous membrane, for example, a battery separator. For example, the microporous membrane may be any polyethylene battery separator manufactured now or in the future by Daramic® or any other lead-acid battery separator manufacturer.

[0103] In a preferred embodiment, the porous membrane is preferably a microporous membrane, mesoporous membrane, or macroporous membrane having pores of less than about 1 micron, made of natural or synthetic materials, such as polyolefins, polyethylene, polypropylene, phenolic resins, PVC, rubber, synthetic wood pulp (SWP), glass fibers, cellulose fibers, or a combination thereof. More preferably, the porous membrane is a microporous membrane made of a thermoplastic polymer. A preferred microporous membrane may have a pore diameter of about 0.1 μm (100 nanometers) and a porosity of about 60%. The thermoplastic polymer may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. Preferred thermoplastic polymers include polyvinyl and polyolefin. Polyvinyl includes, for example, polyvinyl chloride (PVC). Polyolefins include, for example, polyethylene, such as ultra-high molecular weight polyethylene (UHMWPE), and polypropylene. One preferred embodiment may include a mixture of a filler (e.g., silica) and UHMWPE.

[0104] In some embodiments, the pore diameter of the porous membrane is less than 5 μm, preferably less than 1 μm. Preferably, more than 50% of the pores are approximately 0.5 μm or less. It may be preferable that at least 90% of the pores have a diameter of approximately 0.9 μm or less. The microporous separator preferably has an average pore diameter in the range of approximately 0.05 μm to approximately 0.9 μm, and in some cases, approximately 0.1 μm to approximately 0.3 μm.

[0105] Pore ​​size can, in some cases, be measured using the mercury intrusion method described in Ritter, HL, and Drake, LC, Ind.Eng.Chem.Anal.Ed., 17,787 (1945). This method involves injecting mercury into pores of different sizes by varying the pressure acting on the mercury using a porosimeter (porosimeter model 2000, Carlo Erba). The pore distribution can be determined by evaluating the crude data using MILESTONE 200 software.

[0106] In a particular exemplary embodiment, the porous membrane 200 comprises a back web 202 which may have an array of one or more ribs 204, 206 extending from one or both of the main surfaces. When the porous membrane 200 is provided in a typical lead-acid cell, the back web 202 typically has a positive electrode facing surface 202p and a negative electrode facing surface 202n. Referring to Figures 13A to 15B, the exemplary porous membrane is described and defined by a set of typical dimensions relating to the back web and ribs, although not all of them necessarily are.

[0107] Referring to Figure 13A, the exemplary porous membrane 200 comprises a back web 202 having a longitudinal direction drawn by a vertical arrow line labeled "md" and a width direction drawn by a horizontal arrow line labeled "cmd". The porous membrane 200 further comprises an array of positive electrode ribs 204 extending from the surface facing the positive electrode 202p when installed in a lead-acid cell. The positive electrode ribs 204 are substantially aligned longitudinally in the longitudinal direction md. The array of positive electrode ribs 204 are substantially equally spaced transversely across the width direction cmd. Pos They are separated by a rib 204. The rib 204 may be a positive electrode rib 204. Referring here to Figure 13B, the exemplary porous membrane 200 comprises a back web 202 having a longitudinal direction drawn by a vertical arrow line labeled "md" and a width direction drawn by a horizontal arrow line labeled "cmd". The porous membrane 200 further comprises an array of negative electrode ribs 206 extending from the negative electrode, which faces the surface 202n when installed in a lead-acid cell. The negative electrode ribs 206 are substantially aligned transversely in the width direction cmd and may be referred to as cross negative electrode ribs 206. The array of negative electrode ribs 204 are substantially equally spaced longitudinally across the longitudinal direction md. Neg They are separated by a barrier.

[0108] Referring to Figure 14A, the exemplary porous membrane 200 comprises a back web 202 having a back web thickness, dimensioned as a back web. The porous membrane 200 further comprises an array of positive electrode ribs 204 oriented toward the surface 202p, extending from the positive electrode and substantially aligned in the longitudinal direction md. The positive electrode ribs 204 have a base W Pos Rib base width as dimensioned; tip W Pos Rib tip width; height as dimensions: Pos The positive electrode rib height and spacing are dimensioned as follows: Pos The ribs are spaced as follows. The porous membrane 200 also comprises an array of negative electrode ribs 206 extending from the surface 202n, the porous membrane. The negative electrode ribs 206 have a height NegThe negative electrode rib height is dimensioned as and is substantially aligned in the width direction cmd. Finally, the porous membrane has a back web thickness which is the back web thickness and a positive electrode rib height which is the height Pos , and the height which is the height of the negative electrode rib Neg It is defined by the overall thickness, which is dimensioned as a whole and is equal to the sum of the base W. Referring here to Figure 14B, an exemplary porous membrane 200 which is substantially identical to that shown in Figure 14A has a base W which is the negative electrode rib base width. Neg The tip width of the negative electrode rib is W. Neg , and the spacing between the negative electrode ribs. Neg To further prepare.

[0109] Referring to Figure 15A, the exemplary porous membrane 200 comprises a back web 202 having a back web thickness, dimensioned as a back web. The porous membrane 200 further comprises an array of positive electrode ribs 204 oriented toward the surface 202p, extending from the porous membrane, and substantially aligned in the longitudinal direction md. The positive electrode ribs 204 have a base W Pos Rib base width as dimensioned; tip W Pos Rib tip width; height as dimensions: Pos The positive electrode rib height and spacing are dimensioned as follows: Pos The ribs are spaced as follows. The porous membrane 200 also comprises an array of negative electrode ribs 206 extending from the surface 202n, the porous membrane. The negative electrode ribs 206 have a height Neg The negative electrode rib height is dimensioned as and is substantially aligned in the width direction cmd. Finally, the porous membrane has a back web thickness which is the back web thickness and a positive electrode rib height which is the height Pos , and the height which is the height of the negative electrode rib Neg It is defined by the overall thickness, which is dimensioned as a whole and is equal to the sum of the base W. Referring here to Figure 15B, an exemplary porous membrane 200 which is substantially identical to that shown in Figure 15A has a base W which is the negative electrode rib base width. Neg The tip width of the negative electrode rib is W. Neg , and the spacing between the negative electrode ribs. NegFurthermore, the positive electrode rib 204 is divided into serrations 204s. The positive electrode serrations 204s have a base length L Pos , the tip length of the rib is tip L Pos , and the pitch, which is the pitch between the serrations. Pos It is equipped with.

[0110] In certain selected embodiments of the present invention, any or both arrays of ribs are selected from the group consisting of solid ribs, individual broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs substantially extending in the longitudinal direction of the porous membrane, transverse ribs substantially extending in the width direction of the porous membrane, transverse ribs substantially extending in the width direction of the porous membrane, cross ribs substantially extending in the width direction of the porous membrane, negative electrode cross ribs (NCR), individual teeth or toothed ribs, serrations, serrated ribs, sawtooth or sawtoothed ribs, curved or sinusoidal ribs, arranged in a solid or broken zigzag-like form, grooves, channels, textured areas, embossing, dimples, porous, non-porous, miniribs or cross miniribs, and combinations thereof. One more preferred embodiment of a rib or profile is a positive electrode side serrated rib and a negative electrode side cross rib (NCR). Another, more preferred embodiment of a rib or profile is a positive electrode side longitudinal rib and a negative electrode side cross rib (NCR).

[0111] The overall thickness of the porous or microporous membrane (including back web thickness and rib height) is preferably more than approximately 100 μm and less than or equal to approximately 5.0 mm. The overall thickness of the separator may be in the range of approximately 0.15 mm to approximately 2.5 mm, approximately 0.25 mm to approximately 2.25 mm, approximately 0.5 mm to approximately 2.0 mm, approximately 0.5 mm to approximately 1.5 mm, or approximately 0.75 mm to approximately 1.5 mm. In some cases, the overall thickness of the separator may be approximately 0.8 mm or approximately 1.1 mm.

[0112] Exemplary porous membranes for separator assemblies may be provided as flat sheets, leaves, wraps, sleeves, or as envelopes or pocket separators. An exemplary envelope porous membrane may envelop the positive electrode ("positive electrode envelope separator"), resulting in the porous membrane having two inner sides facing the positive electrode and two outer sides facing the adjacent negative electrode. Alternatively, another exemplary envelope porous membrane may envelop the negative electrode ("negative electrode envelope separator"), resulting in the porous membrane having two inner sides facing the negative electrode and two outer sides facing the adjacent positive electrode. In such an envelope porous membrane, the bottom edge 350 may be a folded or sealed fold edge. Furthermore, the horizontal edges 105a, 105b may be continuous or intermittently sealed seam edges. The edges may be sealed by mechanical means, adhesives, heat, ultrasonic welding, or any combination thereof. It may be glued or sealed by a bond.

[0113] Certain exemplary porous membranes may be processed to form a hybrid envelope. The hybrid envelope may be provided by forming one or more slits or openings before, during, or after the envelope is formed. The length of the openings may be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the total edge length. The length of the openings may be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the total edge length. The hybrid envelope may have 1 to 5 or more openings, 1 to 4, 2 to 4, 2 to 3, or 2 openings, which may or may not be evenly distributed along the length of the bottom edge. It is preferable that there are no openings at the corners of the envelope.

[0114] Some other exemplary embodiments of the porous membrane configuration include: a negative or positive electrode envelope; a negative or positive electrode sleeve; a negative or positive electrode hybrid envelope; and both electrodes may be enveloped or sleeved, or any combination thereof.

[0115] In some embodiments of the present invention, the ribs have a rib height 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, 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, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm, or 3.0 mm.

[0116] In some embodiments of the present invention, the protrusion is a short rib having a rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, or 1.5 mm. The ribs may have widths of approximately 0.005-1.5 mm, 0.01-1.0 mm, 0.025-1.0 mm, 0.05-1.0 mm, 0.075-1.0 mm, 0.1-1.0 mm, 0.2-1.0 mm, 0.3-1.0 mm, 0.4-1.0 mm, 0.5-1.0 mm, 0.4-0.8 mm, or 0.4-0.6 mm.

[0117] The separator may include negative electrode ribs having a height of approximately 25 μm to 250 μm, preferably 50 μm to 125 μm, and more preferably 75 μm, in the longitudinal direction or in the cross direction or in the mini-ribs of the negative electrode.

[0118] In certain embodiments, the projection may include ribs, each having a longitudinal axis positioned at an angle of 0° to less than 180° with respect to the top edge of the separator. In some cases, all ribs in the separator may be positioned at the same angle, while in other embodiments, there may be ribs positioned at different angles. For example, in some embodiments, the separator may include rows of ribs, at least some of which have ribs at an angle θ with respect to the top edge of the separator. All ribs in a single row may have the same suitable angle, while in other cases, a single row may have ribs at different angles.

[0119] In certain cases, the entire surface of the separator includes ribs (e.g., continuous or discontinuous rows of ribs, randomly placed ribs, patterned ribs, or off-center ribs). In other embodiments, certain fragments of the separator surface (discontinuous ribs in the set rows) do not contain ribs. These fragments may occur along any edge of the separator, including the top, bottom, or sides, or toward the center of the separator, and such fragments are encircles on one or more sides that include portions having ribs.

[0120] In various, and more preferably, embodiments, the porous or microporous membrane has a back web on its surface comprising one or more ribs, e.g., serrated, sawtoothed, angled, or broken ribs, or a combination thereof. Preferred ribs may be 8 μm to 1 mm in height and 8 μm to 20 mm apart, while the preferred back web thickness of the microporous polyolefin separator layer (without ribs or embossing) may be about 0.05 mm to about 0.50 mm (for example, about 0.25 mm in a particular embodiment). For example, the ribs may be spaced 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, 0.9 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, 2.0 mm, 2.25 mm, 2.5 mm, 2.75 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or about 10 mm apart. In some embodiments, the ribs may be patterned, for example, at 0° to 90° relative to each other, and may be on one side of the separator layer or on both sides of the polyolefin separator. In some embodiments, the acid-mixed ribs may be forward, positive electrode, or positive electrode side ribs. Various patterns including ribs on both sides of the separator or separator layer may include positive electrode ribs and negative electrode longitudinal or cross ribs, for example, smaller, more densely packed negative electrode longitudinal or cross ribs or mini-ribs, on the second side or back surface of the separator. Such negative electrode longitudinal or cross ribs may, in some cases, be about 0.025 mm to about 0.1 mm in height, preferably about 0.075 mm, but may be 0.25 mm in size. Other patterns may include ribs on both sides of the separator layer having negative electrode mini-ribs (mini-ribs extending in the same direction with respect to the cross direction compared to the main ribs on the other side of the separator) on the second side or back surface of the separator. Such negative electrode mini-ribs may, in some cases, be about 0.025 mm to about 0.25 mm in height, preferably about 0.050 mm to about 0.125 mm.

[0121] The ribs may be serrated in certain preferred embodiments. The serrations may have an average tip length of about 0.05 mm to about 1 mm. For example, the average tip length may be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or about 0.9 mm or more; and / or about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or about 0.1 mm or less.

[0122] The serrations may have an average base length of approximately 0.05 mm to approximately 1 mm. For example, the average base length may be approximately 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 approximately 0.9 mm or more; and / or approximately 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 approximately 0.1 mm or less.

[0123] When serrations are present, they may have an average height of approximately 0.05 mm to approximately 4 mm. For example, the average height may be approximately 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 approximately 0.9 mm or more; and / or approximately 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 approximately 0.1 mm or less. In embodiments where the serration height is the same as the rib height, the serrated rib also protrudes. This range is sometimes referred to as the "part." This range may apply to separators for industrial traction-type start / stop batteries, where the overall thickness of the separator may typically be about 1 mm to about 4 mm, as well as to separators for automotive start / stop batteries, where the overall thickness of the separator may be less (for example, typically about 0.3 mm to about 1 mm).

[0124] The serrations may have an average center-to-center pitch of approximately 0.1 mm to approximately 50 mm. For example, the average center-to-center pitch may be approximately 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 approximately 1.5 mm or more; and / or approximately 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 approximately 0.2 mm or less.

[0125] The serrations may have an average height-to-base width ratio of approximately 0.1:1 to approximately 500:1. For example, the average height-to-base width ratio may be approximately 0.1:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, or 450:1 or more; and / or approximately 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, or 25:1 or less.

[0126] The serrations may have an average base width to tip width ratio of approximately 1000:1 to approximately 0.1:1. For example, the average base width to tip width ratio can be approximately 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 or higher, and / or it could be approximately 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or less than 1:1.

[0127] In some embodiments, the separator may have dimples. Dimples are typically protruding features or projections on one or more surfaces of the separator. The thickness of the dimples may be 1 to 99% of the thickness of the separator. For example, the average thickness of the dimples may be about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or less than 5% of the thickness of the separator. The dimples may be arranged in rows along the separator. The rows or lines may be spaced about 1 μm to about 10 mm apart. For example, the rows may be spaced approximately 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, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, 2.0 mm, 2.25 mm, 2.5 mm, 2.75 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm apart. In contrast, the dimples may be arranged in a random array or in a random form.

[0128] The dimples may have an average dimple length of approximately 0.05 mm to approximately 1 mm. For example, the average dimple length may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more; and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0129] The dimples may have an average dimple width of approximately 0.01 mm to approximately 1.0 mm. For example, the average dimple width may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more; and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0130] The dimples may have an average center-to-center pitch of approximately 0.10 mm to approximately 50 mm. For example, the average center-to-center pitch may be approximately 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 or more; and / or approximately 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 or less.

[0131] The dimples may be of a quadrilateral shape, e.g., square and rectangular. The dimples may have an average dimple length to dimple width ratio of approximately 0.1:1 to approximately 100:1. For example, the average length to base width ratio may be approximately 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 above, and / Alternatively, the ratios may be approximately 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or less than 1:1.

[0132] In some embodiments, the dimples may be substantially circular. Circular dimples may have a diameter of about 0.05 to about 1.0 mm. For example, the average dimple diameter may be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more; and / or about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0133] Various other shapes of dimples may also be included. For example, such dimples may be triangles, pentagons, hexagons, heptagons, octagons, ovals, ellipses, and combinations thereof.

[0134] In some embodiments, the separator may be characterized by ribs, serrations, dimples, or a combination thereof. For example, the separator may have a series of serrated ribs running along the separator from top to bottom, and a second series of serrated ribs running horizontally along the separator. In other embodiments, the separator may have alternating arrangements of serrated ribs, dimples, continuous, interrupted, or broken solid ribs, or a combination thereof.

[0135] Membrane composition In certain embodiments, the improved separator may include a porous membrane that can be used as a separator alone or in combination with a fibrous mat, in particular as a lead-acid battery separator, and such separator may consist of: a natural or synthetic substrate; a plasticizer for processing; a filler; one or more natural or synthetic rubbers and / or latex, the rubbers and / or latex being cured or crosslinked, or uncured or uncrosslinked; one or more other additives and / or coatings, such as surfactants, antioxidants, etc.; and any of these. It can consist of combinations.

[0136] Base material In certain embodiments, exemplary natural or synthetic substrates may include: polymers; thermoplastic polymers; phenolic resins; natural or synthetic rubbers; synthetic wood pulp; lignin; glass fibers; synthetic fibers; cellulose fibers; and any combination thereof. In certain preferred embodiments, the exemplary separator may be a porous membrane made of a thermoplastic polymer. Exemplary thermoplastic polymers may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers may include polyvinyl and polyolefin. In certain embodiments, polyvinyl may include, for example, polyvinyl chloride ("PVC"). In certain preferred embodiments, polyolefins may include, for example, polyethylene, polypropylene, ethylene-butene copolymer, and any combination thereof, but polyethylene is preferred. In certain embodiments, exemplary natural or synthetic rubbers may include, for example, latex, uncured or uncrosslinked rubber, crosslinked or cured rubber, crumb or crushed rubber, and combinations thereof.

[0137] Polyolefins In certain embodiments, the porous membrane layer preferably comprises a polyolefin, specifically polyethylene. Preferably, the polyethylene is high molecular weight polyethylene ("HMWPE") (e.g., polyethylene having a molecular weight of at least about 600,000). More preferably, such polyethylene is ultra-high molecular weight polyethylene ("UHMWPE"). Exemplary UHMWPE may have a molecular weight of at least about 1,000,000, particularly greater than about 4,000,000, most preferably about 5,000,000 to about 8,000,000, as measured by viscosity measurement and calculated by Margolies' equation. Furthermore, exemplary UHMWPE may have a standard load melt index of substantially zero (0), as measured using a standard load of 2,160 g as specified in ASTM D 1238 (condition E). Furthermore, the exemplary UHMWPE may have a viscosity number of approximately 600 ml / g or more, preferably approximately 1,000 ml / g or more, more preferably approximately 2,000 ml / g or more, and most preferably approximately 3,000 ml / g or more, as determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C.

[0138] rubber Novel porous membranes and / or fibrous mats disclosed herein may contain latex and / or rubber. As used herein, rubber means rubber, latex, natural rubber, synthetic rubber, uncured or uncrosslinked rubber, crosslinked or cured rubber, crumb or crushed rubber, or mixtures or combinations thereof. Exemplary natural rubber may contain one or more blends of polyisoprene commercially available from various suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber and silicone rubber and copolymer rubber, such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber ("EPM" and "EPDM") and ethylene / vinyl acetate rubber. The rubber may be crosslinked or uncrosslinked; in certain preferred embodiments, the rubber is uncrosslinked. In certain embodiments, the rubber may be a blend of crosslinked and non-crosslinked rubber.

[0139] plasticizer In certain embodiments of porous membranes, exemplary processing plasticizers may include processing oils, petroleum, paraffinic mineral oils, mineral oils, and any combination thereof. Typically, exemplary embodiments utilize a plasticizer while extruding a substrate to form a membrane, sheet, or web. After the formation of the porous membrane, the plasticizer is extracted, leaving a small amount of residual plasticizer, such as residual oil.

[0140] Filler The separator may contain a filler having a high structural morphology. Examples of fillers include: silica, dry fine silica; precipitated silica; amorphous silica; highly crushable silica; alumina; talc; fish meal; fish bone meal; carbon; carbon black; and combinations thereof. In a particular preferred embodiment, the filler is one or more silica particles. High structural morphology refers to an increased surface area. The filler may be, for example, about 100 m².2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 170m 2 / g, 180m 2 / g, 190m 2 / g, 200m 2 / g, 210m 2 / g, 220m 2 / g, 230m 2 / g, 240m 2 / g, or 250m 2 It can have a high surface area of ​​over 100 m² / g. In some embodiments, the filler (e.g., silica) is about 100 m². 2 / g~about 300m 2 / g, approx. 125m 2 / g ~ approx. 275m 2 / g, approx. 150m 2 / g ~ approx. 250m 2 / g, or preferably about 170m 2 / g ~ approx. 220m 2It may have a surface area of ​​1 / g. The surface area can be evaluated using TriStar 3000™ for multipoint BET nitrogen surface area. A high structural morphology allows the filler to retain more oil during the manufacturing process. For example, fillers with a high structural morphology have a high level of oil absorption, e.g., about 150 ml / 100g, 175 ml / 100g, 200 ml / 100g, 225 ml / 100g, 250 ml / 100g, 275 ml / 100g, 300 ml / 100g, 325 ml / 100g, or more than 350 ml / 100g. In some embodiments, the filler (e.g., silica) may have an oil absorption capacity of approximately 200 ml / 100g to approximately 500 ml / 100g, approximately 200 ml / 100g to approximately -400 ml / 100g, approximately 225 ml / 100g to approximately 375 ml / 100g, approximately 225 ml / 100g to approximately 350 ml / 100g, approximately 225 ml / 100g to approximately 325 ml / 100g, preferably approximately 250 ml / 100g to approximately 300 ml / 100g. In some cases, a silica filler having an oil absorption capacity of approximately 266 ml / 100g is used. Such a silica filler has a water content of approximately 5.1% and approximately 178 ml 2 It has a BET surface area of ​​approximately 23 μm, an average particle size of approximately 0.1% sieve residue (230 mesh value), and a bulk density of approximately 135 g / L.

[0141] Silica, which has a relatively high oil absorption capacity and a relatively high affinity for plasticizers (e.g., mineral oil), is preferably dispersible in a mixture of polyolefin (e.g., polyethylene) and plasticizer when forming exemplary lead-acid battery separators of the type shown herein. Previously, some separators have suffered from the disadvantage of insufficient dispersibility caused by silica aggregation when using large amounts of silica to produce such separators or membranes. In at least some specific separators of the present invention shown and described herein, the polyolefin, e.g., polyethylene, forms a shish-kebab structure because there are fewer silica aggregates or clumps that inhibit the molecular motion of the polyolefin when the molten polyolefin is cooled. All of this contributes to improved permeability of the resulting separator membrane, and the formation of the shish-kebab structure or morphology means that mechanical strength is maintained or even improved while a separator with a lower overall ER is produced.

[0142] In some selected embodiments, the filler (e.g., silica) has an average particle size of about 25 μm or less, and in some cases, about 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm or less. In some cases, the average particle size of the filler particles is about 15 μm to about 25 μm. The particle size of the silica filler and / or the surface area of ​​the silica filler are determined by the silica filling. This contributes to the oil absorption capacity of the agent. The silica particles in the final product or separator may be within the size range described above. However, the initial silica used as a raw material may form as one or more aggregates and / or agglomerates, which may have a size of approximately 200 μm or larger.

[0143] In some preferred embodiments, the silica used to produce the separator of the present invention has an increased amount or number of surface silanol groups (surface hydroxyl groups) compared to silica fillers previously used to produce lead-acid battery separators. For example, a silica filler that may be used in certain preferred embodiments herein may have at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, or at least about 35% more silanol groups and / or hydroxyl surface groups compared to known silica fillers used to produce known polyolefin lead-acid battery separators.

[0144] The ratio of silanol groups (Si-OH) to silicon elements (Si) (i.e., (Si-OH) / Si) can be measured, for example, as follows:

[0145] 1. A porous polyolefin membrane (a specific membrane of the present invention contains a specific variety of oil-absorbing silica according to the present invention) is freeze-pulverized and subjected to solid-state nuclear magnetic resonance spectroscopy ( 29 Prepare a powdered sample for Si-NMR.

[0146] 2. For powdered samples 29 Perform Si-NMR and observe the spectra including the spectral intensity of Si directly bonded to the hydroxyl group (spectrums: Q2 and Q3) and the spectral intensity of Si directly bonded only to the oxygen atom (spectrum: Q4). The molecular structure of each NMR peak spectrum can be depicted as follows: Q2: (SiO)2-Si * -(OH)2: Contains two hydroxyl groups Q3: (SiO)3-Si * -(OH): Contains one hydroxyl group • Q4: (SiO)4-Si * : All Si bonds are SiO Here, Si * This is an element that has been proven by NMR observation.

[0147] 3. Used for observation 29 The conditions for Si-NMR are as follows: ·Equipment: Bruker BioSpin Avance 500 ·Resonance frequency: 99.36MHz • Sample amount: 250 mg • NMR tube: 7mφ • Observation method: DD / MAS • Pulse width: 45° • Repeat time: 100 seconds • Scans: 800 • Magic Angle Spinning: 5,000Hz • Chemical shift standard: -22.43 ppm for silicone rubber

[0148] 4. Numerically separate the spectral peaks and calculate the area ratio of each peak belonging to Q2, Q3, and Q4. Then, based on the ratio, calculate the molar ratio of hydroxyl groups (-OH) directly bonded to Si. The numerical peak separation conditions are as follows: • Fitting range: -80 to -130 ppm • Initial peak tops: -93 ppm in Q2, -101 ppm in Q3, and -111 ppm in Q4, respectively. • First half-width: 400Hz for Q2, 350Hz for Q3, and 450Hz for Q4, respectively. • Gaussian function ratio: 80% initially, then 70-100% during fitting.

[0149] 5. The peak area ratios of Q2, Q3, and Q4 (totaling 100) are calculated based on each peak obtained by fitting. The NMR peak area corresponds to the number of molecules in each silicate bond structure (therefore, the NMR peak of Q4 has 4 Si-O-Si bonds in the silicate structure; the NMR peak of Q3 has 3 Si-O-Si bonds in the silicate structure and 1 Si-OH bond; and the NMR peak of Q2 has 2 Si-O-Si bonds in the silicate structure and 2 Si-OH bonds). Thus, the number of hydroxyl groups (-OH) in Q2, Q3, and Q4 are multiplied by 2 (2), 1 (1), and zero (0), respectively. These three results are summed up. The summed value represents the molar ratio of hydroxyl groups (-OH) directly bonded to Si.

[0150] In certain embodiments, silica may be in the range of approximately 21:100 to 35:100, in some preferred embodiments, approximately 23:100 to approximately 31:100, in certain preferred embodiments, approximately 25:100 to approximately 29:100, and in other preferred embodiments, at least approximately 27:100 or more. 29 It may have a molecular ratio of OH groups to Si groups (i.e., OH / Si) as measured by Si-NMR.

[0151] In some selected embodiments, the use of the above-mentioned fillers allows for the use of a higher percentage of processing oil during the extrusion step. When the porous structure in the separator is formed in part by the removal of oil after extrusion, a higher initial oil absorption results in a higher porosity or higher void capacity. Although processing oil is an essential component of the extrusion step, the oil is a non-conductive component of the separator. The residual oil in the separator protects the separator from oxidation when in contact with the positive electrode. The precise amount of oil in the processing step can be controlled in the manufacture of conventional separators. Generally speaking, conventional separators are manufactured using about 50% to about 70% processing oil, in some embodiments about 55% to about 65%, in some embodiments about 60% to about 65%, and in some embodiments about 62% processing oil. The percentages are on a weight basis relative to the weight of other base materials (e.g., polymers, fillers, etc.). It is known that reducing the oil to less than about 59% causes combustion due to increased friction against the components of the extruder. However, increasing the oil content beyond a specified amount can cause shrinkage during the drying phase, leading to dimensional instability. Previous attempts to increase the oil content resulted in pore contraction or compression during oil removal, but the separators prepared as disclosed herein exhibit minimal pore contraction or compression, if any, during oil removal. Thus, the porosity can be increased without compromising pore diameter and dimensional stability, thereby reducing electrical resistance.

[0152] In certain selected embodiments, the use of the above-described filler allows for a reduced final oil concentration in the finished separator. Since oil is a nonconductor, a reduction in oil content can increase the ionic conductivity of the separator and help lower the electrical resistance ("ER") of the separator. Thus, a separator with reduced final or residual oil content may have increased efficiency. In certain selected embodiments, films are provided having a final or residual processing oil content (by weight) of less than about 20%, for example, about 14% to about 20%, and in some specific embodiments, about 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, or less than 5%.

[0153] The filler can further reduce what is called the hydration layer of electrolyte ions and improve the transport of such ions across the membrane, thereby lowering the overall ER of the battery, such as an enhanced liquid cell battery or system.

[0154] The filler(s) may contain various types (e.g., polar types, e.g., metals) that facilitate the flow of electrolytes and ions across the separator. This also leads to a reduction in overall electrical resistance when such a separator is used in a liquid-type battery, such as an enhanced liquid-type battery.

[0155] Crushable In certain selected embodiments, the filler may be alumina, talc, silica, or a combination thereof. In some embodiments, the filler may be precipitated silica, and in some embodiments, the precipitated silica may be amorphous silica. In some embodiments, it is preferable to use silica aggregates and / or lumps, which reduce bending and electrical resistance by allowing fine dispersion of the filler throughout the separator. In certain preferred embodiments, the filler (e.g., silica) is characterized by a high level of fracturability. Good fracturability improves the dispersion of the filler throughout the polymer during the extrusion of the porous membrane, thereby improving the porosity and, by extension, the overall ionic conductivity through the separator.

[0156] Fragility can be measured as the likelihood, tendency, or propensity of silica particles or material (aggregates or aggregates) to break into smaller, more dispersible particles, fragments, or components. As shown on the left side of Figure 30, new silica is more fragile than standard silica (breaking into smaller fragments after 30 seconds and 60 seconds of sonication). For example, new silica had a 50% volume particle size of 24.90 μm at 0 seconds of sonication, 5.17 μm at 30 seconds, and 0.49 μm at 60 seconds. Thus, there was a size (diameter) reduction of over 50% of 50% of silica particles after 30 seconds of sonication and over 75% after 60 seconds. Therefore, one more preferred definition of "high fragility" may be a reduction of at least 50% in average size (diameter) of silica particles after 30 seconds of ultrasonic treatment and at least 75% in average size (diameter) after 60 seconds of ultrasonic treatment (in the treatment of a resin-silica mixture for film formation). In at least one particular embodiment, it may be preferable to use more fragile silica, and it may be even more preferable to use silica that is fragile and multimodal in its fragility, for example, bimodal or trimodal. Referring to Figure 30, standard silica shows single-modal fragility or particle size distribution, while new silica appears to be more fragile, showing bimodal (two peaks) after 30 seconds of ultrasonic treatment and trimodal (three peaks) after 60 seconds of ultrasonic treatment. Such fragile and multimodal particle size silica(s) can impart improved film and separator properties.

[0157] The use of a filler having one or more of the above characteristics enables the production of separators with higher final porosity. Separators disclosed herein may have final porosity of about 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or greater than 70%. Porosity may be measured using the gas adsorption method. Porosity may be measured by BS-TE-2060.

[0158] In some selected embodiments, the porous separator may have a higher proportion of larger pores while maintaining an average pore diameter of approximately 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, or 0.1 μm or less.

[0159] According to at least one embodiment, the separator consists of polyethylene, such as ultra-high molecular weight polyethylene ("UHMWPE"), mixed with a processing oil and a filler, as well as any desired additives. According to at least one other embodiment, the separator consists of a processing oil and It consists of ultra-high molecular weight polyethylene (UHMWPE) mixed with talc. According to at least one other embodiment, the separator consists of UHMWPE mixed with a processing oil and silica, for example, precipitated silica, for example, amorphous precipitated silica. The additive can then be applied to the separator via one or more of the above techniques.

[0160] In addition to reduced electrical resistance and increased cold cranking amplifier, preferred separators are also designed to provide other benefits. Regarding assembly, separators pass through processing equipment more easily and are therefore manufactured more efficiently. For faster assembly and to prevent short circuits during subsequent lifespan, separators have superior puncture strength and oxidation resistance compared to standard PE separators. Combined with reduced electrical resistance and increased cold cranking amplifier, battery manufacturers can easily find improved and sustained electrical performance in batteries with these new separators.

[0161] Additives / Surfactants In certain embodiments, the exemplary separator may have additives added to the separator or porous membrane that improve one or more performance aspects. The performance-improving additives may be surfactants, wetting agents, colorants, antistatic additives, antimony-inhibiting additives, UV-protective additives, antioxidants, and any combination thereof. In certain embodiments, the surfactant additive may be ionic, cationic, anionic, or nonionic surfactants.

[0162] In certain embodiments described herein, reduced amounts of anionic or nonionic surfactants are added to the porous membrane or separator of the present invention. As a result of the lower amount of surfactant, desirable characteristics may include reduced total organic carbon ("TOC") and / or reduced volatile organic compounds ("VOCs").

[0163] Certain preferred surfactants are nonionic, while other preferred surfactants are anionic. The additive may be a single surfactant, or two or more surfactants, for example, two or more anionic surfactants, two or more nonionic surfactants, or a mixture of at least one ionic surfactant and at least one nonionic surfactant. Certain preferred surfactants may have an HLB value of less than 6, preferably less than 3. The combined use of these certain preferred surfactants with the separators of the present invention described herein may result in a further improved separator that, when used in a lead-acid battery, produces reduced moisture loss, reduced antimony poisoning, improved cycling, reduced float current, reduced float potential, or any combination thereof in the lead-acid battery. Suitable surfactants include surfactants such as alkyl sulfate salts; alkylaryl sulfonate salts; alkylphenol-alkylene oxide adducts; soaps; alkyl-naphthalene-sulfonate salts; one or more sulfosuccinates, such as anionic sulfosuccinates; dialkyl esters of sulfosuccinate salts; amino compounds (primary, secondary, tertiary, or quaternary amines); block copolymers of ethylene oxide and propylene oxide; various polyethylene oxides; and salts of mono and dialkyl phosphate esters. Additives include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicon surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters, and sucrose esters of fatty acids.

[0164] In a particular embodiment, the additive may be represented by formula (I). [ka] During the ceremony: R is a linear or non-aromatic hydrocarbon radical having 10 to 4200 carbon atoms, preferably 13 to 4200, which may be interrupted by oxygen atoms; [ka] or [ka] Preferably H, and k=1 or 2; M is an alkali metal or alkaline earth metal ion, H + or NH4 + Therefore, all variable values ​​M are simultaneously H + It does not mean; n = 0 or 1; m = 0 or an integer between 10 and 200; x = 1 or 2.

[0165] In the compound according to formula (I), the ratio of oxygen atoms to carbon atoms is in the range of 1:1.5 to 1:30, and m and n cannot be 0 at the same time. However, preferably only one of the variable values ​​n and m is different from 0.

[0166] Non-aromatic hydrocarbon radicals are intended to be radicals that do not contain aromatic groups or that represent aromatic groups themselves. Hydrocarbon radicals may be interrupted by oxygen atoms (i.e., they may contain one or more ether groups).

[0167] R is preferably a linear or branched aliphatic hydrocarbon radical that may be interrupted by an oxygen atom. A saturated, non-crosslinked hydrocarbon radical is quite particularly preferred. However, as described above, R may contain an aromatic ring in certain embodiments.

[0168] Through the use of the compound of formula (I) in the manufacture of battery separators, protection against oxidative degradation can be efficiently achieved.

[0169] A battery separator containing a compound according to formula (I) is preferred, where: R is a hydrocarbon radical having 1 to 60, preferably 1 to 20, and quite particularly preferably 1 to 8 oxygen atoms, 10 to 180, preferably 12 to 75, and quite particularly preferably 14 to 40 carbon atoms, and is especially preferably a hydrocarbon radical of the following formula: [ka] During the ceremony: 〇R 2 R is an alkyl radical having 10 to 30 carbon atoms, preferably 12 to 25, and particularly preferably 14 to 20 carbon atoms. 2 For example, it may contain an aromatic ring and be linear or nonlinear; P is an integer between 0 and 30, preferably between 0 and 10, and particularly preferably between 0 and 4; 〇q is an integer between 0 and 30, preferably between 0 and 10, and particularly preferably between 0 and 4; Compounds in which the sum of p and q is 0 to 10, and especially 0 to 4, are particularly preferred; n=1; m=0.

[0170] formula [ka] This should be understood to include compounds with arrangements of groups different from those shown in the square brackets. For example, according to the compounds of the present invention, those in which the radicals in the brackets are formed by alternating (OC2H4) and (OC3H6) groups are preferred.

[0171] R 2 Additives that are linear or branched alkyl radicals having 10 to 20, preferably 14 to 18 carbon atoms, have proven particularly advantageous. OC2H4 preferably represents OCH2CH2, and OC3H6 preferably represents OCH(CH3)2 and / or OCH2CH2CH3.

[0172] Preferred additives include alcohols, with primary alcohols (p=q=0;m=0) being particularly preferred, and among primary alcohols, fatty alcohol ethoxylates (p=1-4, q=0), fatty alcohol propoxylates (p=0;q=1-4), and fatty alcohol alkoxylates (p=1-2;q=1-4) ethoxylates are preferred. Fatty alcohol alkoxylates can be achieved, for example, through the reaction of the corresponding alcohol with ethylene oxide or propylene oxide.

[0173] Additives of type m=0 that are insoluble or merely sparingly soluble in water and sulfuric acid have proven particularly advantageous.

[0174] Additives containing a compound according to formula (I) are also preferred, where: R is an alkane radical having 20 to 4200, preferably 50 to 750, and quite preferably 80 to 225 carbon atoms; M is an alkali metal or alkaline earth metal ion, H + or NH4 + In particular, alkali metal ions, for example, Li + na + and K + or H + Therefore, all variable values ​​M are simultaneously H + It does not mean; n=0; m is an integer between 10 and 200; x = 1 or 2.

[0175] Manufacturing of porous membranes In some embodiments, exemplary porous membranes may be produced by mixing components in an extruder. For example, about 5% to about 15% by weight of a polymer (e.g., polyethylene, UHMWPE, etc.), about 10% to about 75% by weight of a filler (e.g., silica), about 10% to about 85% of a processing oil, and optionally about 1% to about 50% by weight of rubber and / or latex may be mixed in the extruder. The exemplary porous membrane may be produced by passing the components through a heated extruder, passing the extruded material through a mold, and passing it through a nip formed by two heated presses or calender stacks or rolls to form a continuous web. A considerable amount of processing oil can be extracted from the web using a solvent. The web may then be dried, slit into lanes of a predetermined width, and then wound onto a roll. In addition, the press or calender roll may have various groove patterns engraved on it (or the embossing roll may have raised elements) to substantially represent the ribs, grooves, textured areas, and embossing described herein. These can be imparted. The amounts of rubber, fillers, oils, and polymers are all balanced with respect to drivability and desirable separator properties, such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, and flexure.

[0176] In addition to being added to the components of the extruder, certain embodiments combine the rubber with the porous membrane after extrusion. For example, the rubber may be coated on one or both sides, preferably on the side facing the negative electrode, with a liquid slurry consisting of rubber and / or latex, optionally silica, and water, and then dried so that a film of this material forms on the surface of an exemplary porous membrane. For better wetting of this layer, a wetting agent may be added to the slurry used in the lead-acid cell. In certain embodiments, the slurry may also contain one or more performance-enhancing additives described herein. After drying, the porous layer and / or film is formed on the surface of the separator, adheres very well to the porous membrane, and increases electrical resistance only non-significantly, if any. After the rubber is added, it may be further compressed using either a mechanical press or a calender stack or rolls. Another possible method of applying rubber and / or latex is to apply the rubber and / or latex slurry to one or more surfaces of the separator by dipping coating, roller coating, spray coating, or curtain coating, or any combination thereof. These processes may be carried out before or after the extraction of the processing oil, or before or after slits are formed in the lane.

[0177] Further embodiments of the present invention include depositing rubber onto a film by impregnation and drying.

[0178] Manufacturing using performance-enhancing additives In certain embodiments, performance-enhancing additives, such as surfactants, wetting agents, colorants, antistatic additives, antioxidants, and any combination thereof, may also be mixed with the other components in the extruder. The porous membrane according to this disclosure may then be extruded into the shape of a sheet or web to be completed in substantially the same manner as described above.

[0179] In certain embodiments, in addition to or alternatively to an extruder, additives may be applied to the separator porous membrane, for example, when completed (e.g., after extracting the bulk of the processing oil and before or after introducing the rubber). According to certain preferred embodiments, an additive or a solution of an additive (e.g., an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for the application of non-thermally stable additives and additives that are soluble in the solvents used for the extraction of the processing oil. Particularly suitable as solvents for the additives according to the invention are low molecular weight alcohols such as methanol and ethanol, and mixtures of these alcohols with water. Such application can be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides. Such application may also be carried out during the extraction of the pore-forming agent (e.g., processing oil) while in the solvent bath. In certain selected embodiments, some portions of performance-improving additives, such as surfactant coatings or performance-improving additives (or both) added to the extruder before the separator is fabricated, may bind to antimony in the battery system, and may inactivate it, and / or may form a compound with it, and / or may cause it to fall into the battery sludge residue, and / or may prevent its deposition on the negative electrode. The surfactant or additive may also be added to the electrolyte, glass mat, battery case, pasting paper, pasting mat, etc., or combinations thereof.

[0180] In certain exemplary embodiments, an additive (e.g., an ionic surfactant, cationic surfactant, non-ionic surfactant, anionic surfactant, or a combination thereof) is at least about 0.5 g / m 2 , 1.0 g / m 2 , 1.5 g / m 2 , 2.0 g / m 2 , 2.5 g / m 2 , 3.0 g / m 2 , 3.5 g / m 2 , 4.0 g / m 2 , 4.5 g / m 2 , 5.0 g / m 2 , 5.5 g / m2 , 6.0 g / m 2 , 6.5 g / m 2 , 7.0 g / m 2 , 7.5 g / m 2 , 8.0 g / m 2 , 8.5 g / m 2 , 9.0 g / m 2 , 9.5 g / m 2 or 10.0 g / m 2 or even up to about 25.0 g / m 2 of surface area density (i.e., grams per surface area of the separator) or additive level may be present. The additive is from about 0.5 g / m 2 to about 15 g / m 2 , from about 0.5 g / m 2 to about 10 g / m 2 , from about 1.0 g / m 2 to about 10.0 g / m 2 , 1.5 g / m 2 to about 10.0 g / m 2 , 2.0 g / m 2 to about 10.0 g / m 2 , from about 2.5 g / m 2 to about 10.0 g / m 2 , from about 3.0 g / m 2 to about 10.0 g / m 2 , from about 3.5 g / m 2 to about 10.0 g / m 2 , from about 4.0 g / m 2 to about 10.0 g / m 2 , from about 4.5 g / m 2 to about 10.0 g / m 2 , from about 5.0 g / m 2 to about 10.0 g / m 2 , from about 5.5 g / m 2 to about 10.0 g / m 2 , from about 6.0 g / m 2 to about 10.0 g / m 2 , from about 6.5 g / m 2 to about 10.0 g / m 2 , from about 7.0 g / m 2 to about 10.0 g / m 2 , from about 7.5 g / m 2 to about 10.0 g / m 2 , from about 4.5 g / m 2 to about 7.5 g / m 2, about 5.0g / m 2 ~Approx. 10.5g / m 2 , about 5.0g / m 2 ~Approx. 11.0g / m 2 , about 5.0g / m 2 ~Approx. 12.0g / m 2 , about 5.0g / m 2 ~Approx. 15.0g / m 2 , about 5.0g / m 2 ~Approx. 16.0g / m 2 , about 5.0g / m 2 ~Approx. 17.0g / m 2 , about 5.0g / m 2 ~Approx. 18.0g / m 2 , about 5.0g / m 2 ~Approx. 19.0g / m 2 , about 5.0g / m 2 ~About 20.0g / m 2 , about 5.0g / m 2 ~Approx. 21.0g / m 2 , about 5.0g / m 2 ~Approx. 22.0g / m 2 5.0g / m 2 ~Approx. 23.0g / m 2 , about 5.0g / m 2 ~Approx. 24.0g / m 2 , or 5.0 g / m 2 ~Approx. 25.0g / m 2 It may be present in the separator at a surface area density or add-on level.

[0181] The above application may also be carried out by immersing the battery separator in the additive or a solution of the additive (solvent bath application) and removing the solvent as needed (e.g., by drying). Thus, the application of the additive may be combined with extraction, which is often applied, for example, during film formation. Other preferred methods include spraying the additive onto the surface and applying one or more additives as a dip coating, roller coating, or curtain coating to the surface of the separator.

[0182] In certain embodiments described herein, reduced amounts of ionic, cationic, anionic, or nonionic surfactants are added to the separator of the present invention. In such cases, desirable features may include reduced total organic carbon and / or reduced volatile organic compounds (attributable to the lower amount of surfactant), and a desirable separator of the present invention can be produced according to such embodiments.

[0183] Purpose The exemplary separators described herein may be used in a variety of exemplary batteries. Such batteries may be any lead-acid battery, e.g., liquid lead-acid batteries, reinforced liquid lead-acid batteries, plate batteries, tubular batteries, valve-regulated lead-acid ("VRLA") batteries, gel batteries, absorbent glass mat ("AGM") batteries, deep-cycle lead-acid batteries, and / or batteries that operate in a partially charged state. Such batteries may be used in a variety of exemplary applications, for example, in vehicles, alternative energy integration and storage, e.g., solar and wind energy generation and other renewable and / or alternative energy sources, inverters, uninterruptible power supply ("UPS") devices, etc. The exemplary vehicles described herein are, but are not limited to, vehicles that include at least one of the separators or batteries described herein. In preferred embodiments, exemplary vehicles may be automobiles, trucks, motorcycles, all-terrain vehicles, motorcycles, forklifts, golf carts, wheelchairs, idle-start-stop ("ISS") vehicles, hybrid vehicles, hybrid electric vehicles, micro HEVs, electric vehicles, batteries for electric rickshaws, electric tricycles, electric bicycles, ships, or any other electric vehicle. Exemplary batteries in which preferred embodiments of the separator of the present invention may be used include: plate batteries, liquid lead-acid batteries, and Flooded lead-acid batteries ("EFB"), controlled valve lead-acid ("VRLA") batteries, gel batteries, absorbent glass mat ("AGM") batteries, deep cycle batteries, tubular batteries, inverter batteries, vehicle batteries, starting-lighting-ignition ("SLI") vehicle batteries, idling-start-stop ("ISS") vehicle batteries, automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, wheelchair batteries, marine batteries, etc. can be mentioned.

[0184] In some preferred embodiments, the battery is used in a device that operates in a partially charged state. For example, the battery is used in a device that operates in a partially charged state under normal daily conditions (i.e., in a normal use state rather than a misuse state).

[0185] Method The methods described herein are not overly limited. The method may be a method for preventing acid replacement in a lead-acid battery, a flooded lead-acid battery, or a flooded lead-acid battery that is intended to operate or be operated in a partially charged state under normal use conditions rather than misuse. The method may be a method for providing the electrode array described herein in a lead-acid battery.

[0186] Various embodiments of the present invention are described in achieving various objects of the present invention. It should be recognized that these embodiments merely illustrate the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

[0187] Conclusion According to at least selected embodiments, the present disclosure or invention relates to separators, particularly separators for liquid lead-acid batteries, that can have reduced or mitigated oxygen deficiency; reduced or mitigated acid formation; reduced or mitigated dendrite growth; and reduced electrical resistance, and / or increased cold cranking amplifier. Also disclosed herein are methods, systems, and battery separators for improving battery life; reducing or mitigating oxygen deficiency; reducing or mitigating acid formation; reducing or mitigating dendrite growth; reducing the effects of oxidation; reducing moisture loss; reducing internal resistance; increasing wettability; improving acid diffusion; improving cold cranking amplifier; improving uniformity, and any combination thereof, in at least enhanced liquid lead-acid batteries. According to at least specific embodiments, the present disclosure or invention relates to improved separators for enhanced liquid lead-acid batteries, the separators include improved and novel rib designs, and improved separator resilience. In at least certain embodiments, the present disclosure or invention relates to an improved separator for an enhanced liquid lead-acid battery, comprising performance-enhancing additives or coatings, increased oxidation resistance, increased porosity, increased void capacity, amorphous silica, highly oil-absorbing silica, highly silanol-group silica, silica with an OH-to-Si ratio of 21:100 to 35:100, shish kebab structure or form, polyolefin microporous membrane (a membrane and polymer, e.g., containing particulate filler in an amount of 40% by weight or more of ultra-high molecular weight polyethylene ("UHMWPE"), having shish kebab formations with expanded chain crystals (shishi formation) and folded chain crystals (kebab formation), and kebab formations with an average repeat period of 1 nm to 150 nm), reduced sheet thickness, reduced flex, reduced thickness, reduced oil content, increased wetting, increased acid diffusion, and any combination thereof.

[0188] According to at least a first aspect of a particular selected embodiment, the lead-acid battery separator comprises a porous membrane having a polymer and a filler. The porous membrane extends from a first surface The separator comprises at least a first surface having at least a plurality of first ribs. The first plurality of ribs comprises a plurality of first teeth or discontinuous peaks or projections, each of which is close to one another to impart elasticity to the separator. Such elasticity may refer to the separator's ability to resist deflection while under pressure resulting from the swelling of the NAM. Such proximity may be at least approximately 1.5 mm from one tooth, peak, or projection to another. The separator may further comprise a continuous base having a plurality of first teeth or discontinuous peaks or projections extending from the base.

[0189] In certain embodiments, the separator may have a continuous base having a first plurality of teeth or discontinuous peaks or projections extending from the base. The base may be wider than the width of the teeth or discontinuous peaks or projections. The base may also extend continuously between each of the teeth or discontinuous peaks or projections.

[0190] According to at least certain selected embodiments, the separator may comprise ribs that are one or more of the following: solid ribs, individual broken ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, linear ribs, longitudinal ribs substantially extending in the longitudinal direction of the porous membrane, transverse ribs substantially extending in the width direction of the porous membrane, transverse ribs substantially extending in the width direction of the separator, teeth, toothed ribs, serrations, serrated ribs, sawtooth walls, sawtoothed ribs, curved ribs, sinusoidal ribs, arranged in a continuous zigzag-sawtooth shape, arranged in a broken discontinuous zigzag-sawtooth shape, grooves, channels, textured regions, embossing, dimples, cylinders, mini-cylinders, porous, non-porous, mini-ribs, cross-mini-ribs, and combinations thereof.

[0191] At least some of the first plurality of ribs may be defined by an angle that does not have to be parallel or perpendicular to the edge of the separator. Furthermore, the angle may be defined as an angle with respect to the longitudinal direction of the porous membrane, and the angle may be one of the following: greater than zero degrees (0°) and less than 180 degrees (180°) to greater than 180 degrees (180°) and less than 360 degrees (360°). In certain embodiments of the disclosed embodiments, the angle may vary across the plurality of ribs.

[0192] In a particular selected embodiment of the present invention, the first plurality of ribs may have a widthwise spacing pitch of approximately 1.5 mm to approximately 10 mm, and the plurality of teeth or discontinuous peaks or protrusions may have a longitudinal spacing pitch of approximately 1.5 mm to approximately 10 mm.

[0193] In a particular selected embodiment, the separator may comprise a second plurality of ribs extending from a second surface of the porous membrane. The second plurality of ribs may be one or more of the following: solid ribs, individual broken ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, linear ribs, longitudinal ribs substantially extending in the longitudinal direction of the porous membrane, transverse ribs substantially extending in the width direction of the porous membrane, transverse ribs substantially extending in the width direction of the separator, teeth, toothed ribs, sawtooth walls, sawtoothed ribs, curved ribs, sinusoidal ribs, arranged in a continuous zigzag-sawtooth shape, arranged in a broken discontinuous zigzag-sawtooth shape, grooves, channels, textured regions, embossing, dimples, cylinders, mini-cylinders, porous, non-porous, mini-ribs, cross-mini-ribs, and combinations thereof.

[0194] At least some of the second set of ribs may be defined by an angle that does not have to be parallel or perpendicular to the edge of the separator. Furthermore, the angle may be defined as an angle with respect to the longitudinal direction of the porous membrane, and the angle may be one of the following: greater than zero degrees (0°) and less than 180 degrees (180°) to greater than 180 degrees (180°) and less than 360 degrees (360°). In certain embodiments of the disclosed embodiments, the angle varies throughout the set of ribs. That's fine.

[0195] The second set of ribs may have a cross-machine or longitudinal spacing pitch of approximately 1.5 mm to approximately 10 mm.

[0196] The first surface may have one or more ribs having a different height from the first plurality of ribs located adjacent to the edge of the lead-acid battery separator. Similarly, the second surface may have one or more ribs having a different height from the second plurality of ribs located adjacent to the edge of the lead-acid battery separator.

[0197] In a selected embodiment, the polymer may be one of the following: polymers, polyolefins, polyethylene, polypropylene, ultra-high molecular weight polyethylene ("UHMWPE"), phenolic resins, polyvinyl chloride ("PVC"), rubber, synthetic wood pulp ("SWP"), lignin, glass fibers, synthetic fibers, cellulose fibers, and combinations thereof.

[0198] A fibrous mat may be provided. The mat may be one of the following: glass fiber, synthetic fiber, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof; or it may be nonwoven fabric, mesh, fleece, and combinations thereof.

[0199] Furthermore, the separator may be a cut piece, leaf, pocket, sleeve, wrap, fold, envelope, or hybrid envelope.

[0200] According to at least one exemplary embodiment of a particular selection, the separator may be provided with elastic means for reducing the deflection of the separator.

[0201] According to at least a particular selected embodiment, the lead-acid battery comprises a positive electrode and a negative electrode comprising a swollen negative electrode active material. The separator comprises at least a portion of the separator positioned between the positive and negative electrodes. An electrolyte is provided that substantially immerses at least a portion of the positive electrode, at least a portion of the negative electrode, and at least a portion of the separator. In at least a particular selected embodiment, the separator may have a porous membrane comprising at least a polymer and a filler. A first plurality of ribs may extend from the surface of the porous membrane. The ribs may be arranged, for example, to prevent oxygen depletion in the presence of swelling of the NAM. The lead-acid battery may operate under any one or more of the following conditions: in operation, stationary, in backup power applications, in cycling applications, in a partially charged state, and in any combination thereof.

[0202] The rib may have multiple teeth, or discontinuous peaks or projections. Each tooth, or discontinuous peak or projection may be at least approximately 1.5 mm from another of the multiple discontinuous peaks. The continuous base may have multiple teeth, or discontinuous peaks or projections extending from it.

[0203] The first set of ribs may be further provided to improve acid mixing in the battery, particularly during battery operation. The separator may be positioned parallel to the battery's start and stop operations. The separator may comprise a positive electrode, a negative electrode, or a mat adjacent to the separator. The mat may consist at least partially of glass fiber, synthetic fiber, silica, at least one performance-enhancing additive, latex, natural rubber, synthetic rubber, and any combination thereof. The mat may be nonwoven, woven, mesh, fleece, and combinations thereof.

[0204] In at least certain selected embodiments of the present invention, the lead-acid battery may be a flat plate battery, a flooded lead-acid battery, an enhanced flooded lead-acid ( "EFB") battery, a valve-regulated lead-acid ( "VRLA") battery, a deep cycle battery, a gel battery, an absorbent glass mat ( "AGM") battery, a tubular battery, an inverter battery, a vehicle battery, a starting-lighting-ignition ( "SLI") vehicle battery, an idling-start-stop ( "ISS") vehicle battery, an automotive battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric vehicle battery, an electric scooter battery, or an electric bicycle battery, or any combination thereof.

[0205] In certain embodiments, the battery may operate at a depth of discharge of from approximately 1% to approximately 99%.

[0206] According to at least one embodiment, a microporous separator with reduced tortuosity is provided. Tortuosity refers to the degree of curvature / rotation of pores along their length. Thus, a microporous separator with reduced tortuosity presents a shorter path for ions to move through the separator, thereby reducing the electrical resistance. The microporous separator according to such an embodiment may have a reduced thickness, an increased pore diameter, more interconnected pores, and / or more open pores.

[0207] According to at least certain selected embodiments, microporous separators having increased porosity, or separators having different pore structures and / or reduced thickness, wherein the porosity is not significantly different from that of known separators. Ions move more rapidly through the microporous separator having the optimized porosity, optimized pore capacity, optimized bending, and / or reduced thickness, thereby reducing electrical resistance. Such reduced thickness may result in a reduction in the overall weight of the battery separator, which in turn reduces the weight of the enhanced liquid battery in which the separator is used, which in turn reduces the overall weight of the vehicle in which the enhanced liquid battery is used. Such reduced thickness may alternatively result in an increase in the space for positive electrode active material ("PAM") or negative electrode active material ("NAM") in the enhanced liquid battery in which the separator is used.

[0208] According to at least certain selected embodiments, a microporous separator with increased wettability (in water or acid) is provided. The separator with increased wettability is more accessible to ionic species of the electrolyte, thereby facilitating their passage across the separator and reducing electrical resistance.

[0209] According to at least one embodiment, a microporous separator with reduced final oil content is provided. Such a microporous separator also facilitates a reduction in ER (electrical resistance) in an enhanced liquid battery or system.

[0210] The separator may contain an improved filler that has increased crushability and can increase the porosity, pore size, internal pore surface area, wetting properties, and / or surface area of ​​the separator. In some embodiments, the improved filler has a higher structural morphology and / or reduced particle size and / or a different amount of silanol groups than previously known fillers, and / or is more hydroxylated than previously known fillers. The improved filler can absorb more oil and / or allow for the incorporation of more processing oil during separator formation without shrinkage or compression in parallel when the oil is removed after extrusion. The filler can further reduce what is called the hydration layer of electrolyte ions and improve the transport of these across the membrane, thereby further reducing the electrical resistance or overall ER of the battery, e.g., an enhanced liquid battery or system.

[0211] The filler(s) may contain various types (e.g., polar types, e.g., metals) that increase ion diffusion and facilitate the flow of electrolytes and ions across the separator. This also leads to a reduction in overall electrical resistance when such a separator is used in a liquid-type battery, such as an enhanced liquid-type battery.

[0212] Microporous separators further include novel and improved pore morphologies and / or novel and improved fibril morphologies such that when such separators are used in liquid lead-acid batteries, the separators contribute to a significant reduction in the electrical resistance in such liquid lead-acid batteries. Such improved pore morphologies and / or fibril morphologies may result in separators in which the pores and / or fibrils are suitable for a shish-kebab (or shish-kebab) type morphology. Another means of describing novel and improved pore shapes and structures is a textured fibril morphology in which silica nodes or silica nodes are present in kebab-type formations in polymer fibrils (fibrils sometimes called shish) within the battery separator. In addition, in certain embodiments, the silica structure and pore structure of the separator according to the present invention may be described as a skeletal structure, vertebral structure, or spinal structure, where the silica nodes in the polymer kebab along the polymer fibrils resemble vertebrae or intervertebral discs ("kebabs"), and in some cases may be oriented substantially perpendicular to elongated central vertebrae or fibrils (extended chain polymer crystals) that approximate a spine-like shape ("shishi").

[0213] In some cases, improved batteries including improved separators having improved pore and / or fibril morphologies may exhibit electrical resistance 20% lower, in some cases 25% lower, in some cases 30% lower, and in some cases even more than 30% lower (they can reduce the internal resistance of the battery), while such separators maintain and preserve the balance of other important desirable mechanical properties of lead-acid battery separators. Furthermore, in certain embodiments, the separators described herein have novel and / or improved pore shapes such that more electrolyte flows through or fills the pores and / or voids compared to known separators.

[0214] Furthermore, the Disclosure provides an improved enhanced liquid lead-acid battery comprising one or more improved battery separators for an enhanced liquid battery, wherein the separator combines, with respect to the battery, desirable features of reduced acid layering, reduced voltage drop (or increased voltage drop endurance), and increased CCA, in some cases more than 8%, more than 9%, or in some embodiments more than 10%, or more than 15% increased CCA. Such improved separators may result in an enhanced liquid battery whose performance matches or even exceeds that of an AGM battery. Such low electrical resistance separators may also be treated to result in an enhanced liquid lead-acid battery having reduced moisture loss.

[0215] The separator may contain one or more performance-enhancing additives, such as surfactants, in combination with other additives or agents, residual oil, and fillers. Such performance-enhancing additives can reduce oxidation of the separator and / or further facilitate ion transport across the membrane, which contributes to a reduction in the overall electrical resistance of the enhanced liquid cell described herein.

[0216] The lead-acid battery separator described herein may include a polyolefin microporous membrane, which comprises: a polymer, e.g., polyethylene, e.g., ultra-high molecular weight polyethylene, particulate filler, and processing plasticizer (optionally together with one or more additional additives or agents). The polyolefin microporous membrane may contain particulate filler in an amount of 40% by weight or more of the membrane. The ultra-high molecular weight polyethylene may also be expanded in multiple ways. The shish kebab formation, which includes chain-like crystals (shishi formation) and a plurality of folded chain-like crystals (kebab formation), may contain a polymer, and the average repeat or periodicity of the kebab formation is 1 nm to 150 nm, preferably 10 nm to 120 nm, more preferably 20 nm to 100 nm (at least in the rib-side portion of the separator).

[0217] The average repeatability or periodicity of the kebab formation is calculated by the following definition: The surface of the polyolefin microporous film is subjected to metal deposition, and then observed using a scanning electron microscope ("SEM"). Images of the surface are then taken at a magnification of, for example, 30,000 or 50,000 times with an accelerating voltage of 1.0 kV. • In the same visual cortex of the SEM image, at least three regions are shown where shish kebab formations extend continuously for a length of at least 0.5 μm. Then, the periodicity of the kebabs in each shown region is calculated. The periodicity of the kebab is identified by the Fourier transform of the concentration profiles (contrast profiles) obtained from the vertical protrusion of shish kebab formations relative to shish formations in each indicated region, and the average of the repeating periods is calculated. • Analyze the images using a general analysis tool, such as MATLAB® (R2013a). • In the spectral profile obtained after the Fourier transform, profiles detected in the short-wavelength region are considered noise. Such noise is mainly caused by deformation of the contrast profile. The contrast profile obtained for the separator according to the present invention appears to generate a square wave (rather than a sinusoidal wave). Furthermore, when the contrast profile is a square wave, the Fourier transform profile becomes a sinusoidal function, thus generating multiple peaks in the short-wavelength region in addition to the main peak that shows the periodicity of the true kebab. Such peaks in the short-wavelength region can be detected as noise.

[0218] In some embodiments, the lead-acid battery separators described herein include a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica; 29 The molecular ratio of OH groups to Si groups in the above-mentioned filler, as measured by Si-NMR, is in the range of 21:100 to 35:100, 23:100 to 31:100 in some embodiments, 25:100 to 29:100 in some embodiments, and 27:100 or higher in certain preferred embodiments.

[0219] Silanol groups alter the silica structure from crystalline to amorphous because the relatively rigid Si-O covalent bond network partially disappears. Amorphous silica, such as Si(-O-Si)2(-OH)2 and Si(-O-Si)3(-OH), has many strains that can function as various oil absorption sites. Therefore, oil absorption increases as the amount of silanol groups (Si-OH) increases with respect to silica. In addition, the separators described herein may exhibit increased hydrophilicity and / or have higher void capacity and / or have certain aggregates surrounded by large voids when they contain silica with a larger amount of silanol groups and / or hydroxyl groups than known lead-acid battery separators.

[0220] The microporous separator further includes novel and improved pore morphologies and / or novel and improved fibril morphologies such that when such separator is used in a liquid lead-acid battery, the separator contributes to significantly reducing the electrical resistance in such a liquid lead-acid battery. Such improved pore morphologies and / or fibril morphologies may result in a separator in which the pores and / or fibrils are suitable for a shish-kebab (or shish-kebab) type morphology. Another means of describing the novel and improved pore shapes and structures is a textured separator in which silica nodes or silica nodes are present in kebab-type formations in polymer fibrils (fibrils sometimes called shish) within the battery separator. It is in a fibril form. In addition, in certain embodiments, the silica structure and pore structure of the separator according to the present invention may be described as a skeletal structure or vertebral structure or spine structure, where the silica nodes in the polymer kebab along the polymer fibrils resemble vertebrae or intervertebral discs ("kebabs"), and in some cases may be oriented substantially perpendicular to elongated central vertebrae or fibrils (extended chain polymer crystals) that approximate a spine-like shape ("shishi").

[0221] In certain selected embodiments, the vehicle may be equipped with a lead-acid battery as generally described herein. The battery may further be equipped with a separator as described herein. The vehicle may be an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart, a hybrid vehicle, a battery for a hybrid electric vehicle, an electric vehicle, an idle-start-stop ("ISS") vehicle, an electric rickshaw, an electric bicycle, a battery for an electric bicycle, and a combination thereof.

[0222] In certain preferred embodiments, the present disclosure or invention provides a flexible battery separator (a porous membrane of polymer, e.g., polyethylene, and a separator having certain amounts of performance-enhancing additives and ribs) whose components and physical properties and characteristics synergistically combine to meet, and in certain embodiments exceed, the previously known flexibility performance currently used in many deep-cycle battery applications, thereby addressing, in an unexpected way, previously unmet requirements in the deep-cycle battery industry. In particular, the separators of the present invention described herein are more robust, less brittle, less brittle, and more stable over time (less prone to degradation) than separators conventionally used in deep-cycle batteries. The flexible, performance-enhancing additive-containing, and rib-containing separators of the present invention combine the desired robust physical and mechanical properties of polyethylene separators with the capabilities of conventional separators, while also improving the performance of battery systems using them.

[0223] According to at least selected embodiments, aspects, or purposes, novel or improved separators, battery separators, reinforced liquid battery separators, batteries, cells, and / or methods for manufacturing and / or using such separators, battery separators, reinforced liquid battery separators, cells, and / or batteries are disclosed or provided herein. According to at least certain embodiments, the disclosure or invention relates to novel or improved battery separators for reinforced liquid batteries. Also disclosed herein are methods, systems, and battery separators having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, the disclosure or invention relates to an improved separator for reinforced liquid batteries, having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, or any combination thereof. According to at least certain embodiments, separators are provided that include or indicate reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least certain embodiments, separators are provided for plate batteries, tubular batteries, battery applications for vehicle SLI, and HEV ISS applications, deep cycle applications, batteries for golf carts or golf carts and electric rickshaws, batteries operating in a partially charged state ("PSOC"), inverter batteries; and storage batteries for renewable energy sources, and any combination thereof.

[0224] In certain exemplary embodiments, the lead-acid battery comprises an electrode array having one or more negative electrodes and one or more positive electrodes arranged alternately between the one or more negative electrodes. At least one of the electrodes is enveloped by a fibrous mat, and one or more positive electrodes adjacent to at least one of the one or more negative electrodes are enveloped by a porous membrane. The porous membrane may be a microporous battery separator.

[0225] In exemplary embodiments, the fibrous mat may be a nonwoven fabric, mesh, fleece, and / or a combination thereof. The fibrous mat may further be glass fiber, pulp, polymer, and / or a combination thereof. The fibrous mat may also be formed from a polymer, and in addition, from glass fiber, pulp, and / or a combination thereof, and the polymer may be polyolefin, polyester, polyamide, polyimide, and / or a combination thereof. The fibrous mat may be an inorganic material, such as silica. The fibrous mat may be a spun-bonded-melt-nonwoven composite material or a carbon fiber nonwoven material, and the like.

[0226] An exemplary porous membrane may comprise one or more arrays of ribs on at least one of its surfaces, or one or more arrays of ribs on two of its surfaces. The ribs may have a height of about 10 μm to about 2.0 mm. The porous membrane may be one or more of the following: natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and / or combinations thereof. Alternatively, the porous membrane may be polyethylene, silica, and processing oil, where the processing oil is present in an amount of about 5% to about 15% by weight of the porous membrane.

[0227] In a particular selected embodiment, the porous membrane has a porosity greater than approximately 55%, approximately 60%, or approximately 65%.

[0228] In another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be enveloped around the positive electrode and sealed on one side, two sides, and / or three sides of the positive electrode.

[0229] In another exemplary embodiment, the fibrous mat of the exemplary lead-acid battery may be enveloped around the negative electrode and sealed on one, two, and / or three sides of the negative electrode.

[0230] In another exemplary embodiment, a preferred lead-acid battery may include an electrode array comprising one or more negative electrodes and one or more positive electrodes arranged alternately between the one or more negative electrodes. The battery may further include a fibrous mat assembly comprising one or more electrodes and a fibrous mat at least partially integrated with at least one of the negative electrodes. The porous membrane may be a microporous membrane and may envelope one or more of the one or more electrodes and the fibrous mat assembly, or at least one of the one or more positive electrodes adjacent to the one or more electrodes and the fibrous mat assembly. In exemplary embodiments, the fibrous mat may be integrated with the active material to about 2% to about 50%, about 5% to about 25%, about 5% to about 20%, or about 10% to about 15% of the mat thickness of the fibrous mat.

[0231] Any exemplary fibrous mat may be one or more of nonwoven fabrics, meshes, fleeces, and / or combinations thereof. Alternatively, the fibrous mat may be one or more of glass fibers, pulp, polymers, and / or combinations thereof. Furthermore, the fibrous mat may be formed from a polymer, and in addition, from one or more of glass fibers, pulp, and / or combinations thereof, wherein the polymer may be one or more of polyolefins, polyesters, polyamides, polyimides, and / or combinations thereof.

[0232] In another embodiment of the exemplary lead-acid battery, the exemplary fibrous mat may be an inorganic material, such as silica. The fibrous mat may be a spun-bonded melt nonwoven fabric, a carbon fiber nonwoven fabric, and the like.

[0233] In a further embodiment of the exemplary lead-acid battery, the exemplary porous membrane may have one or more arrays of ribs on one or two of its surfaces. The ribs of one or more arrays of ribs may have a height of about 10 μm to about 2.0 mm.

[0234] Exemplary porous membranes may be at least one of natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and / or combinations thereof. In one particular embodiment, the porous membrane may be polyethylene, silica, and processing oil.

[0235] In another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be enveloped around the positive electrode and sealed on one, two, and / or three sides of the positive electrode. In yet another exemplary embodiment, the porous membrane of the exemplary lead-acid battery may be sealed on one, two, and / or three sides of one or more electrodes and fibrous mat assemblies.

[0236] In a further selected embodiment of an exemplary preferred embodiment, the lead-acid battery comprises an electrode array of one or more negative electrodes and one or more positive electrodes arranged alternately with respect to one another. A porous membrane envelope is further provided, enveloping at least one of the one or more negative electrodes located therein, wherein the porous membrane includes ribs on one or more of its surfaces, and a fibrous mat is disposed within the envelope. The ribs may be at least partially on the surface of the porous membrane adjacent to the fibrous mat. The ribs may have a height of about 10 μm to about 2.0 mm, or about 5 μm to about 300 μm, or about 25 μm to about 200 μm. The fibrous mat may also envelop at least one of the one or more negative electrodes. Furthermore, the fibrous mat may be at least partially integrated with the negative electrode.

[0237] Alternatively, the fibrous mat may be a separate piece positioned between the ribs and may have a thickness of about 50% to about 150% of the rib height. In a selected embodiment of the present invention, the fibrous mat may be positioned between the negative electrode and the porous membrane. The fibrous mat may be one or more of glass fibers, pulp, polymers, and combinations thereof. The fibrous mat may be formed from a polymer in combination with one or more of glass fibers, pulp, and combinations thereof; where the polymer may be one or more of polyolefins, polyesters, polyamides, polyimides, and combinations thereof. The fibrous mat may also be an inorganic material, such as silica. The fibrous mat may be a spun-bonded-melt-nonwoven composite material or a carbon fiber nonwoven material.

[0238] In a selected embodiment, the porous membrane may have ribs on two of its surfaces. The porous membrane may also be one or more of the following: natural materials, synthetic materials, polyolefins, phenolic resins, polyvinyl chloride (PVC), natural rubber, synthetic rubber, synthetic wood pulp, glass fibers, lignin, cellulose fibers, and combinations thereof. Specifically, the porous membrane may be polyethylene, silica, and processing oil.

[0239] In a selected embodiment of the present invention, the porous membrane may be sealed on one side of the negative electrode, two sides of the negative electrode, or three sides of the negative electrode. Alternatively, the fibrous mat may be sealed on one side of the negative electrode, two sides of the negative electrode, and three sides of the negative electrode.

[0240] In a selected embodiment of the present invention, the system comprises a vehicle utilizing one or more batteries substantially described herein. The vehicle may be an automobile, truck, motorcycle, all-terrain vehicle, forklift, golf cart, hybrid vehicle, hybrid electric vehicle, electric vehicle, idle-start-stop ("ISS") vehicle, electric rickshaw battery, electric tricycle, electric bicycle, wheelchair, or ship.

[0241] In selected embodiments, the lead-acid batteries substantially described herein may be plate batteries, liquid lead-acid batteries, reinforced liquid lead-acid batteries ("EFB"), valve-regulated lead-acid ("VRLA") batteries, gel batteries, absorbent glass mat ("AGM") batteries, deep-cycle batteries, tubular batteries, inverter batteries, vehicle batteries, start-light-ignition ("SLI") vehicle batteries, idle-start-stop ("ISS") vehicle batteries, automobile batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, wheelchair batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, or marine batteries.

[0242] In an optional embodiment, the method is provided for preventing or mitigating acid displacement in a lead-acid battery, liquid lead-acid battery, or liquid lead-acid battery that is operated in or intended to be operated in a partially charged state. The method may include manufacturing a battery having substantially the same structure as any of the batteries described herein.

[0243] Novel or improved systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, electrodes, and / or methods for manufacturing and / or using such batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, fibrous mats, cells, and / or electrodes as shown or described herein.

[0244] Novel or improved batteries, in particular lead-acid batteries described and / or indicated herein; novel or improved systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, electrodes, and / or methods for manufacturing and / or using such systems, vehicles, batteries, enhanced liquid lead-acid batteries, deep-cycle batteries, separators, battery separators, enhanced liquid lead-acid battery separators, deep-cycle battery separators, separators, fibrous mats, cells, and / or electrodes; improved batteries having improved lead-acid battery separators, and / or improved methods for using such batteries having such improved separators; in lead-acid batteries, improving battery life, reducing battery failure, reducing moisture loss, reducing float current, reducing increase in internal resistance, increasing wettability, reducing acid layering, improving acid diffusion, and active material Methods, systems, processes, and battery separators for preserving, reducing delamination of active material, and / or improving uniformity; improved lead-acid battery separators comprising an improved functional coating, improved battery separators for reducing acid layering, improved battery separators for improving acid diffusion, improved lead-acid batteries for preserving active material, improved lead-acid battery separators for reducing delamination of active material, improved lead-acid batteries comprising such improved separators, long-life automotive lead-acid batteries, improved liquid lead-acid batteries, and / or batteries having reduced acid layering, improved acid diffusion, improved active material preservation capability, and / or improved active material delamination reduction capability; batteries having a polyethylene separator and a negative electrode with a fibrous mat placed between them, and / or methods for manufacturing and / or using such batteries; batteries having a porous membrane and a fibrous mat laminated thereon, wherein the fibrous mat is adjacent to the negative electrode in such batteries, and / or A method for manufacturing and / or using a light-powered battery. In certain embodiments, it may be preferable that the fibrous mat is attached to the polymer film (e.g., to its ribs, e.g., to the negative electrode ribs), and that the fibrous mat is not embedded in the back web of the film.

[0245] As described herein, exemplary separators may be used in lead-acid batteries used in a variety of applications. Such applications may include, for example: partially charged applications; deep cycle applications; automotive applications; truck applications; motorcycle applications; power applications, e.g., fork trucks, golf carts (also called golf trolleys), etc.; electric vehicle applications; hybrid electric vehicle ("HEV") applications; ISS vehicle applications; electric rickshaw applications; electric tricycle applications; electric bicycle applications; boat applications; and energy storage applications, e.g., renewable and / or alternative energy storage, e.g., wind energy, solar energy, etc. Furthermore, exemplary separators may be used in a variety of batteries. Such exemplary batteries may include, for example: liquid lead-acid batteries, e.g., enhanced liquid lead-acid batteries; AGM batteries; VRLA batteries; plate batteries; tubular batteries; partially charged batteries; deep cycle batteries; automotive batteries; truck batteries; motorcycle batteries; power batteries, e.g., fork truck batteries, golf cart batteries (also called golf carts), etc.; electric vehicle batteries; hybrid electric vehicle ("HEV") batteries; ISS vehicle batteries; electric rickshaw batteries; electric tricycle batteries; electric bicycle batteries; boat batteries; energy storage and energy integration batteries, e.g., renewable and / or alternative energy storage and energy integration and storage, e.g., wind energy, solar energy, etc.

[0246] According to at least selected embodiments, the present disclosure or invention covers novel or improved separators for lead-acid batteries, such as liquid lead-acid batteries, in particular enhanced liquid lead-acid batteries ("EFB"), and various other lead-acid batteries, such as gel and absorbent glass mat ("AGM") batteries. According to at least selected embodiments, the present disclosure or invention covers novel or improved separators, battery separators, resilient separators, balanced separators, EFB separators, batteries, cells, systems, methods, vehicles using the same, methods for manufacturing the same, uses the same, and combinations thereof. Also disclosed herein are methods, systems, and battery separators for improving battery life and reducing battery failure by reducing oxygen deficiency in battery electrodes.

[0247] Liquid lead-acid batteries and vehicles comprising the same are described herein. A liquid lead-acid battery includes an electrode array comprising one or more negative and one or more positive plates arranged alternately and interspersed with respect to one another. In some embodiments, a negative plate is wrapped around or enveloped by a fibrous mat, and a porous membrane is wrapped around or enveloped around adjacent positive plates. In some embodiments, the fibrous mat is at least partially integrated with the negative plate, and the porous membrane is enveloped around the negative plate to which the fibrous mat is at least partially integrated or around adjacent positive plates. In other embodiments, the negative plate is enveloped by a porous membrane having ribs, and the fibrous mat is located between the wrapped negative plate and the porous membrane enveloping the negative plate. Methods, systems, and vehicles utilizing the disclosed batteries are also provided.

[0248] According to at least selected embodiments, the Disclosure or Invention covers novel or improved separators, battery separators, enhanced liquid battery separators, batteries, cells, and / or methods for manufacturing and / or using such separators, battery separators, enhanced liquid battery separators, cells, batteries, systems, methods, and / or vehicles using them. According to at least certain specific embodiments, the Disclosure or Invention covers novel or improved battery separators, resilient separators, balanced separators, liquid lead-acid battery separators, or enhanced liquid lead-acid battery separators, for example, those useful in deep-cycle and / or partially charged ("PSoC") applications. Such applications are not limited to such applications. Examples of typical applications include: electric power applications, e.g., forklifts and golf carts (sometimes referred to as golf trolleys), electric rickshaws, electric bicycles, electric tricycles, etc.; automotive applications, e.g., start-light-ignition ("SLI") batteries, e.g., those used in internal combustion engine vehicles; batteries for idle start-stop ("ISS") vehicles; hybrid vehicle applications, hybrid-electric vehicle applications; batteries requiring high power output, e.g., uninterruptible power supplies ("UPS") or valve-regulated lead-acid batteries ("VRLA"), and / or batteries requiring high CCA; inverters; and energy storage systems, e.g., renewable and / or alternative energy systems, e.g., those found in solar and wind power systems.

[0249] According to at least selected embodiments, the present disclosure or invention relates to separators, resilient separators, balanced separators, particularly separators for liquid lead-acid batteries, which can have reduced or mitigated oxygen deficiency; reduced or mitigated acid formation; reduced or mitigated dendrite growth; reduced electrical resistance and / or increased cold cranking amplifier; reduced electrical resistance and negative electrode cross ribs; low moisture loss, reduced electrical resistance and / or negative electrode cross ribs; dendrite blocking or prevention performance, features and / or structure; acid mixing prevention performance, features and / or structure; improved negative electrode cross ribs; glass mats on the positive and / or negative electrode sides of PE films, pieces, sleeves, folds, wraps, pockets, envelopes, etc.; glass mats laminated on PE films; and / or combinations or subcombinations thereof.

[0250] Improved separators for lead-acid batteries, improved lead-acid batteries incorporating the improved separator, and exemplary embodiments of systems or vehicles incorporating the improved separator and / or battery are disclosed herein. The lead-acid battery separator comprises a porous membrane having a plurality of ribs extending from the surface. The ribs have a plurality of discontinuous peaks arranged, for example, to provide elastic support to the porous membrane in order to mitigate the effects of oxygen deficiency associated with NAM swelling by resisting the forces exerted by the swelling of NAM. The separator is also provided to allow any operation experienced by the battery housing such separator to be utilized in order to mitigate the effects of acid stratification by facilitating acid mixing. Lead-acid batteries incorporating the provided separator are also provided. Such lead-acid batteries may be liquid lead-acid batteries, enhanced liquid lead-acid batteries, and may be provided to operate in a partially charged state. Systems incorporating such lead-acid batteries, such as vehicles or any other energy storage systems, such as solar or wind energy storage systems, are also provided. Other exemplary embodiments are provided, for example, having one or more of the following: reduced electrical resistance; increased puncture resistance; increased oxidation resistance; increased ability to mitigate the effects of dendrite growth; and other improvements.

[0251] In at least selected embodiments, aspects, or purposes, the present disclosure or invention may address, and / or address, novel or improved separators, battery separators, membranes, separator membranes, reinforced liquid battery separators, fibrous mats, batteries, cells, and / or methods for manufacturing and / or using such separators, battery separators, fibrous mats, reinforced liquid battery separators, cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention relates to novel or improved enhanced liquid lead-acid battery separators, fibrous mats, liquid batteries for deep-cycle applications, and / or enhanced liquid batteries for start-light-ignition ("SLI") batteries, and / or systems, vehicles, etc., including such separators, mats, and batteries, and / or improved methods for manufacturing and / or using such improved separators, mats, cells, batteries, systems, vehicles, etc. According to the present invention, the present disclosure or invention relates to improved separators for enhanced liquid batteries, and / or improved methods for manufacturing and / or using such batteries having such improved separators. According to at least selected embodiments, the present disclosure or invention relates to separators, in particular separators for enhanced liquid batteries having reduced electrical resistance and / or increased cold cranking amplifier. Also disclosed herein are methods, systems and battery separators for improving active material retention, improving battery life, reducing moisture loss, reducing internal resistance, increasing wettability, reducing acid layering, improving acid diffusion, improving cold cranking amplifier, and improving uniformity, at least in enhanced liquid batteries. According to at least certain embodiments, the present disclosure or invention relates to an improved separator for an enhanced liquid cell, comprising one or more performance-enhancing additives or coatings, increased porosity, increased porosity, amorphous silica, highly oil-absorbing silica, highly silanol-group silica, retention of active material in electrodes and / or improved retention, and / or any combination thereof.

[0252] According to at least certain embodiments, the Disclosure or Invention relates to novel or improved separators, battery separators, liquid battery separators, reinforced liquid battery separators, fibrous mats, batteries, cells, and / or methods for manufacturing and / or using such separators, battery separators, fibrous mats, liquid battery separators, reinforced liquid battery separators, cells, and / or batteries. According to at least certain embodiments, the Disclosure or Invention relates to novel or improved reinforced liquid battery separators, fibrous mats, liquid batteries for deep cycle applications, liquid batteries for power applications, liquid batteries for partially charged (PSoC) applications, and / or reinforced liquid batteries, and / or systems, vehicles, etc., including such separators, fibrous mats, and batteries, and / or improved methods for manufacturing and / or using such improved separators, fibrous mats, cells, batteries, systems, vehicles, etc. According to at least certain embodiments, the Disclosure or Invention relates to improved separators for enhanced liquid-type batteries, and / or improved methods for manufacturing and / or using such batteries having such improved separators. According to at least selected embodiments, the Disclosure or Invention relates to separators, in particular separators for enhanced liquid-type batteries having reduced electrical resistance and / or increased cold cranking amplifier. Also disclosed herein are methods, systems, and battery separators for improving active material retention, improving battery life, reducing moisture loss, reducing internal resistance, increasing wetting properties, reducing acid layering, improving acid diffusion, improving cold cranking amplifier, and improving uniformity, at least in enhanced liquid-type batteries. According to at least certain embodiments, the present disclosure or invention relates to an improved separator for an enhanced liquid cell, comprising one or more performance-enhancing additives or coatings, optimized porosity, optimized porosity, amorphous silica, highly oil-absorbing silica, highly silanol-group silica, retention of active material in electrodes and / or improved retention, and / or any combination thereof.

[0253] In at least certain embodiments, the present disclosure or invention relates to an improved separator for liquid or reinforced liquid batteries, which includes an improved construction designed to further reduce moisture loss, reduce maintenance and increase misuse resistance in heavy-duty deep-cycle applications, such as golf carts, renewable energy, floor machinery and towing vehicles.

[0254] Features: • Incorporation of a new polyethylene compound to counteract the effects of antimony migration. The suppression is comparable to that of rubber separators. • Sealing capability for automation of both envelopes or sleeves to provide protection from short circuits. • High oxidation resistance. • High porosity for lower electrical resistance. • Optional glass mat for holding active material We can list some examples.

[0255] As profit: By counteracting the negative effects of antimony poisoning, it overcomes battery life requirements, including superior oxidation resistance and reduced moisture loss. • By enclosing and sleeve-attaching the material in high-speed equipment, on-site failures are reduced while improving manufacturing efficiency and consistency. We can list some examples.

[0256] In at least other specific embodiments, the present disclosure or invention relates to an improved separator for tubular, liquid, or reinforced liquid batteries, which helps extend battery life in power applications through special reduced moisture loss features and a unique profile design. As the operation of the power battery in a partially charged state increases, the separator can increase battery life by helping protect against accelerated grid corrosion and acidification.

[0257] Features: • Rib pattern with serrations • Low moisture loss characteristics • Closer rib pitch One could list them.

[0258] As profit: • Improved acid circulation and improved acid mixing (less acid stratification) • Lower acid substitution • Lower moisture loss • Even spacing between plates, and no upward movement under vibration. • Uniform element compression due to closer rib pitch We can list some examples.

[0259] In selected embodiments, liquid lead-acid batteries and systems, vehicles or devices comprising the same, are described herein. In certain selected embodiments, the liquid lead-acid battery includes an electrode array comprising one or more negative electrode plates and one or more positive electrode plates arranged alternately and interspersed with respect to one another. In some embodiments, the negative electrode plates are wrapped around or enveloped by a fibrous mat, and a porous membrane is wrapped around or enveloped around adjacent positive electrodes. In some embodiments, the fibrous mat is at least partially integrated with the negative electrode plate, and the porous membrane is enveloped around the negative electrode plate to which the fibrous mat is at least partially integrated or around adjacent positive electrode plates. In other embodiments, the negative electrode plates are enveloped by a porous membrane having ribs, and the fibrous mat is located between the wrapped negative electrode plate and the porous membrane enveloping the negative electrode plate. In some embodiments, the positive electrode plates are wrapped around or enveloped by a fibrous mat, and the porous membrane is wrapped around or enveloped around adjacent negative electrodes. In some embodiments, the fibrous mat is at least partially integrated with the positive electrode plate, and the porous membrane is enveloped around the positive electrode plate to which the fibrous mat is at least partially integrated, or around the adjacent negative electrode plate. In other embodiments, the positive and / or negative electrode plates are enveloped by a porous membrane having ribs, and the fibrous mat is wrapped around the positive and / or negative electrode plates and the positive and / or It exists between the negative electrode plate and the porous membrane that envelopes it. In certain embodiments, methods, systems, devices, and / or vehicles utilizing the disclosed separators, plates, mats, membranes, composite mats and membranes, laminated mats and membranes, wound plates, pocketed plates, wound pocketed plates, and / or batteries are also provided.

[0260] According to at least selected embodiments, the Disclosure or Invention covers lead-acid batteries, particularly liquid lead-acid batteries, and separators for various types of lead-acid batteries, such as liquid lead-acid batteries or enhanced liquid lead-acid batteries, having the above. According to at least selected embodiments, the Disclosure or Invention covers novel or improved separators, cells, batteries, and / or methods for manufacturing and / or using such separators, cells, and / or batteries. According to at least certain specific embodiments, the Disclosure or Invention covers improved separators for lead-acid batteries, and / or improved methods for using such batteries having such improved separators. Such batteries may be 6-volt (or 6V) or 12-volt batteries, groups of 12, 18, 24, 30, 36, 42, or 48-volt batteries, groups of 24-volt, 36-volt, 48-volt, 60-volt, 72-volt, or 84-volt batteries, series-wired or parallel-wired battery strings of two or more batteries, and the like. Such lead-acid batteries may be used in combination with one or more capacitors, lithium batteries, fuel cells, etc. Such batteries and battery combinations may be used in a variety of exemplary applications, for example, in vehicles, alternative energy integration and storage, such as solar and wind energy generation and other renewable and / or alternative energy sources, inverters, uninterruptible power supply ("UPS") devices, etc. Also disclosed herein are methods, systems, and battery separators for lead-acid batteries to retain active material, improve battery life, reduce battery failure, reduce moisture loss, improve oxidation stability, improve, maintain, and / or reduce float current, improve end-of-charge (EOC) current, reduce the current and / or voltage required to charge and / or fully charge deep-cycle batteries, minimize the increase in internal electrical resistance, reduce electrical resistance, increase wetting, reduce electrolyte wet-out time, reduce battery formation time, reduce antimony poisoning, reduce acid layering, improve acid diffusion, and / or improve uniformity.According to at least certain embodiments, the Disclosure or Invention relates to an improved lead-acid battery separator comprising one or more improved performance-enhancing additives and / or coatings. According to at least certain embodiments, the disclosed separator is useful in deep-cycle applications, for example, in prime movers or vehicles, and / or stationary machinery or vehicles, such as golf carts, forklifts, inverters, renewable energy systems and / or alternative energy systems, as just a few examples, in photovoltaic and wind power systems; in particular, the disclosed separator is useful in battery systems where deep-cycle and / or partial-charge operation is part of the battery life, and more specifically, in battery systems where additives and / or alloys (e.g., antimony (Sb)) are added to the battery to improve the battery life and / or performance, and / or the battery's ability to operate in deep-cycle and / or partial-charge states.

[0261] The compositions and methods of the appended claims are intended to be examples of several aspects of the claims, and are not limited in scope by the specific compositions and methods described herein; any functionally equivalent compositions and methods are intended to be within the scope of the claims. In addition to those shown and described herein, various modifications of compositions and methods are intended to be within the scope of the appended claims. Furthermore, while only certain representative compositions and method steps are specifically described herein, other combinations of such compositions and method steps, even if not specifically enumerated, are intended to be within the scope of the appended claims. Thus, where steps, elements, components, or combinations of components are explicitly referred to herein or below, While there are combinations, other combinations of steps, elements, components, and constituents are also included, even if not explicitly stated. The terms “comprising” and its variations are used herein as synonymous with “including” and its variations and are open, non-restrictive terms. The terms “comprising” and “including” are used herein to describe various embodiments, but the terms “consisting essentially of” and “consisting of” may be used instead of “comprising” and “including” to provide more specific embodiments of the invention, and these are also disclosed. Unless otherwise stated in the examples, all numbers used herein and in the claims to express quantities of components, reaction conditions, etc., should be understood as at least and should not be interpreted in terms of significant figures and ordinary rounding methods as an attempt to limit the application of the equivalence principle in the claims.

[0262] The present invention may be embodied in other forms without departing from its spirit and essential characteristics, and therefore, the appended claims should be referred to rather than the above specification as indicating the scope of the invention. Components that may be used to carry out the disclosed methods and systems are disclosed. These and other components are disclosed herein, and when combinations, subsets, interactions, groups, etc., of these components are disclosed, specific references to various individual and collective combinations and arrangements of these may not be explicitly disclosed, but each should be understood to be specifically anticipated and described herein for all methods and systems. This applies to all aspects of this application, including, but not limited to, steps in the disclosed methods. Therefore, when there are various additional steps that may be carried out, it should be understood that each of these additional steps may be carried out by any specific embodiment or combination of embodiments of the disclosed methods.

[0263] The above description of the structure and method is provided for illustrative purposes only. Examples disclose exemplary embodiments, including the best form, and are used to enable the practical application of the invention, including the fabrication and use of any device or system and the implementation of any incorporated method. These examples are not intended to be exclusive or to limit the invention to the exact steps and / or forms disclosed, and many modifications and variations are possible in light of the above teachings. The features described herein may be combined in any combination. The steps of the method described herein may be carried out in any physically possible sequence. The patentable scope of the invention is defined by the appended claims and may include other examples that a person skilled in the art can imagine. Such other examples are intended to be within the claims when they have structural elements that are no different from the literal words of the claims, or when they include equivalent structural elements that are not substantially different from the literal words of the claims.

[0264] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as examples of some aspects of the claims. Any functionally equivalent compositions and methods are intended to be within the scope of the claims. In addition to those shown and described herein, various modifications of compositions and methods are intended to be within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps are specifically described herein, other combinations of such compositions and method steps, even if not specifically listed, are intended to be within the scope of the appended claims. Thus, while steps, elements, components, or combinations of components may be explicitly mentioned herein or below, other combinations of steps, elements, components, and components are also explicitly described herein. It is included even if it is not explicitly defined.

[0265] When used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include the plural unless the context otherwise clearly indicates. Ranges may be expressed herein as “about” or “approximately” from one particular value and / or “about” or “approximately” to another particular value. When such ranges are expressed, an alternative embodiment includes that one particular value and / or that other particular value. Similarly, when a value is expressed as an approximation by the preceding use of “about,” it will be understood that the above particular value forms an alternative embodiment. It will be further understood that each endpoint of a range is significant both in relation to the other endpoints and independently of the other endpoints. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that such description encompasses both the cases in which such event or situation occurs and the cases in which it does not occur.

[0266] Throughout the above description and the claims of this specification, the word “comprise” and its variations, e.g., “comprising” and “comprises,” mean “comprises but not limited to,” and are not intended to exclude, for example, other additives, components, integers, or steps. The terms “consisting essentially of” and “consisting "of)" may be used in place of "comprising" and "including" to provide more specific embodiments of the invention, which are also disclosed. "Essential" or "for example" means "an example" and is not intended to convey an indicator of a preferred or ideal embodiment. Similarly, "for example" is used for descriptive or illustrative purposes, not in a restrictive sense.

[0267] Unless otherwise stated, all numbers used in this specification and in the claims to represent geometric shapes, dimensions, etc., should be understood as at least one, and should not be interpreted in terms of significant figures and ordinary rounding methods as an attempt to limit the application of the equivalence principle in the claims.

[0268] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art of the disclosed invention. The publications and materials listed herein are incorporated specifically by reference.

[0269] In addition, the present invention as described herein may preferably be put into practice in the absence of any elements not specifically disclosed herein.

Claims

1. A method for manufacturing a negative electrode plate of a lead-acid battery, This includes forming a negative electrode plate wrapped or enveloped with a fibrous mat by wrapping or enveloping the fibrous mat around it. A method for manufacturing a negative electrode plate, wherein the negative electrode plate contains a negative electrode active material, the negative electrode active material is present in the gaps and pores of the fibrous mat to form a mixture layer, and the mixture layer is formed in a range of 2 to 50% of the thickness of the fibrous mat.

2. The method for manufacturing a negative electrode plate according to claim 1, characterized in that the negative electrode plate is wrapped with the fibrous mat.

3. The method for manufacturing a negative electrode plate according to claim 1, characterized in that the negative electrode plate is enveloped with the fibrous mat.

4. The basis weight of the aforementioned fibrous mat is 50 g / m². ２ ~100g / m ２ The method for manufacturing a negative electrode plate according to claim 1.

5. The basis weight of the fibrous mat is 60 g / m². ２ ~80g / m ２ The method for manufacturing a negative electrode plate according to claim 4.

6. The method for manufacturing a negative electrode plate according to claim 1, wherein the fibers in the fibrous mat are polymers.

7. The method for manufacturing a negative electrode plate according to claim 1, wherein the fibrous mat contains an inorganic material, and the inorganic material contains silica.

8. The method for manufacturing a negative electrode plate according to claim 1, wherein the fibrous mat has a thickness in the range of 100 μm to 900 μm.

9. The method for manufacturing a negative electrode plate according to claim 8, wherein the thickness is in the range of 200 μm to 450 μm.

10. The method for manufacturing a negative electrode plate according to claim 1, wherein the diameter of the fibers in the fibrous mat is 7.2 μm ± 0.5 μm.

11. The method for manufacturing a negative electrode plate according to claim 1, wherein the fibrous mat includes a carbon fiber nonwoven fabric material.

12. The method for producing a negative electrode plate according to claim 1, wherein the fibrous mat contains a gelling agent that helps to resist acid formation.

13. The method for manufacturing a negative electrode plate according to claim 1, wherein the lead-acid battery is selected from the group consisting of a plate battery, an electrolyte lead-acid battery, an enhanced electrolyte lead-acid battery ("EFB"), a valve-regulated lead-acid ("VRLA") battery, a gel battery, an absorbent glass mat ("AGM") battery, a deep-cycle battery, a tubular battery, a power battery, an inverter battery, a PSoC battery, a vehicle battery, a start-light-ignition ("SLI") vehicle battery, an idle-start-stop ("ISS") vehicle battery, a car battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric vehicle battery, a wheelchair battery, an electric rickshaw battery, an electric tricycle battery, an electric bicycle battery, and a marine battery.

14. The method for manufacturing a negative electrode plate according to claim 13, wherein the lead-acid battery is installed in a vehicle that is one selected from the group consisting of automobiles, trucks, motorcycles, all-terrain vehicles, motorcycles, forklifts, golf carts, hybrid vehicles, hybrid electric vehicles, electric vehicles, idle-start-stop ("ISS") vehicles, batteries for electric rickshaws, electric tricycles, electric bicycles, wheelchairs, and ships.

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