Improved separator including fiber mats, lead-acid battery using the same, and related method and system

Abstract

To provide a lead-acid battery separator assembly, and a lead-acid battery including the assembly, which prevent or retard the shedding of active material from an electrode in a reinforced flooded battery.SOLUTION: A lead acid battery separator assembly includes a separator layer, and a nonwoven fiber mat, and the fiber mat is disposed adjacent to the separator layer, and the fiber mat has an electrical resistivity in the range of about 6 mΩ cm2 to about 14 mΩ cm2, an average pore size of less than about 5, and an air permeability in the range of about 1500 l / m2s to about 2500 l / m2s.SELECTED DRAWING: Figure 1A

Description

Technical Field

[0001] Related Art This application claims the priority and benefit of International Application No. PCT / US2017 / 017418, filed on February 10, 2017, which is co-pending and owned by the same owner.

[0002] Technical Field According to at least selected embodiments, the present disclosure or invention is directed to a novel or improved separator, battery separator, liquid battery separator, enhanced liquid battery separator, fiber mat, batteries, cells, and / or methods of manufacturing and / or using such separator, battery separator, fiber mat, enhanced liquid battery separator, cell and / or battery. According to at least certain embodiments, the present disclosure or invention is directed to a novel or improved enhanced liquid lead-acid battery separator, fiber mat, liquid battery for deep cycle applications, and / or enhanced liquid battery, and / or system, vehicle, and / or the like, including such separator, mat or battery, and / or improved methods of manufacturing and / or using such improved separator, mat, cell, battery, system, vehicle, and / or the like. According to at least certain embodiments, the present disclosure or invention is directed to an improved separator for an enhanced liquid battery and / or an improved method of manufacturing and / or using such battery comprising such improved separator. According to at least selected embodiments, the present disclosure or invention is directed to a separator, a liquid battery separator, particularly a separator for an enhanced liquid battery having low electrical resistance and / or high cold cranking amps. Additionally, methods, systems and battery separators for enhancing battery life, reducing water loss, reducing internal resistance, improving wettability, reducing stratification, improving acid diffusion, improving cold cranking amps and / or at least improving uniformity within an enhanced liquid battery are disclosed herein. According to at least certain embodiments, the present disclosure or invention is directed to an improved separator for an enhanced liquid battery, the separator comprising one or more performance enhancing additives or coatings, increased porosity, increased pore volume, amorphous silica, high oil absorption silica, high silanol group silica, retention and / or improved retention of active material on the electrodes and / or any combination thereof.

[0003] According to at least the selected embodiments, the present disclosure or invention is directed to lead-acid batteries, particularly separators for flooded lead-acid batteries, and various lead-acid batteries such as flooded lead-acid batteries or enhanced flooded lead-acid batteries comprising the same. According to at least the selected embodiments, the present disclosure or invention is directed to novel or improved separators, cells, batteries, and / or methods of manufacturing and / or using such separators, cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for lead-acid batteries and / or improved methods of using such batteries comprising such improved separators. Additionally, methods, systems, and battery separators for improving battery life, reducing battery failures, reducing water loss, improving oxidation stability, improving, maintaining, and / or reducing float current, improving end-of-charge (EOC) current, reducing the current and / or voltage required for charging and / or full charge of deep-cycle batteries, minimizing internal electrical resistance increase, reducing electrical resistance, improving wettability, reducing the wetting time of the electrolyte, reducing battery formation time, reducing antimony poisoning, reducing stratification, improving acid diffusion, and / or improving uniformity within lead-acid batteries are disclosed herein. At least According to at least certain embodiments, the present disclosure or invention is directed to an improved separator for a lead-acid battery, where the separator includes one or more improved performance enhancing additives and / or coatings. According to at least certain embodiments, the disclosed separator is useful for deep cycle applications, such as in golf carts, forklifts, inverters, renewable energy systems and / or alternative energy systems, to name but a few, such as transport machines or vehicles and / or stationary machines or vehicles like solar power systems and wind power systems; in particular, the disclosed separator is useful for battery systems where deep cycling and / or partial state of charge operation is part of the battery life, and even more particularly, for battery systems where additives and / or alloys (antimony being a prime example) are added to the battery to improve the battery life and / or performance and / or improve the deep cycling and / or partial state of charge operation ability of the battery.

[0004] According to at least selected embodiments, the present disclosure is directed to an improved lead-acid battery, such as a flooded lead-acid battery, an improved system comprising a lead-acid battery, and / or a battery separator, an improved battery separator, an improved vehicle comprising such a system, a method of manufacture or use, or combinations thereof. According to at least certain embodiments, the present disclosure or invention is directed to an improved flooded lead-acid battery for such a battery, an improved battery separator, mat, composite separator, laminated separator, positive side envelope, negative side envelope, and / or the like, and / or a method of manufacture, testing, or use of such an improved flooded lead-acid battery, or combinations thereof. Additionally, methods, systems, batteries, and / or battery separators for reducing stratification, improving battery life and performance of flooded lead-acid batteries, and operating at a partial state of charge are disclosed herein. BACKGROUND OF THE INVENTION

[0005] Enhanced Flooded Batteries (「EFB」) and Absorbent Glass Mat (「AGM」) batteries have been developed to meet the growing demand for power sources in idle start-stop applications. The EFB system has a structure similar to that of conventional flooded lead-acid batteries, with the positive and / or negative electrodes surrounded by a porous separator and immersed in a liquid electrolyte. On the other hand, the AGM system does not contain free liquid electrolyte. Instead, the electrolyte is absorbed in a glass fiber mat and layered on top of the electrodes. Historically, the AGM system has been used for higher discharge power, better cycle life, and greater cold cranking amperes than flooded battery systems. However, AGM batteries are significantly more expensive to manufacture and are more sensitive to overcharging. Thus, the EFB system remains an attractive option for mobile and stationary power sources in a variety of markets and applications.

[0006] The EFB system can include one or more battery separators that divide, or "separate," the negative electrode from the positive electrode within a lead-acid battery cell. The battery separator can have two main functions. First, the battery separator should maintain the physical separation of the positive electrode from the negative electrode to prevent current flow between the two electrodes. Second, the battery separator should allow for ionic flow between the positive and negative electrodes with minimal resistance. Battery separators can be manufactured from many different materials, but these two opposing functions are satisfied by battery separators manufactured from porous insulators. In this structure, the pores contribute to ionic diffusion between the electrodes, and the non-conductive polymer network prevents electrical short circuits.

[0007] Discharge rate and increased cold cranking amperes (amperes or amps) (「CCA」) Larger EFBs could potentially replace AGM batteries. It has been found that cold cranking amperes correlate with the internal resistance of the battery. Thus, strong It is expected that the cold cranking ampere rate will be increased due to the reduction of the internal resistance of the flooded type battery. Thus, there is a need for a new battery separator and / or battery technology that satisfies and overcomes the problems arising from the current lead-acid battery system, particularly reducing the internal resistance and increasing the cold cranking ampere in enhanced flooded type batteries.

[0008] To reduce fuel consumption and exhaust gas generation, 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 micro HEVs or similar vehicles, the automobile may have an idle start / stop (ISS) function, and the engine can stop at various times during idle start / stop and / or regenerative braking. This increases the vehicle's fuel efficiency but also increases the burden on the battery, which must supply power to auxiliary devices (such as air conditioners, media players, and the like) while the vehicle is not in motion.

[0009] Conventional vehicles (such as automobiles without start / stop performance) may use conventional flooded lead-acid batteries such as starting, lighting, ignition (SLI) lead-acid batteries. Since the engine never stops during use, power is only taken from the battery when the engine is cranked. Thus, the battery usually exists in an overcharged state rather than a partially charged state. For example, such conventional flooded lead-acid batteries can exist in a charged state of more than 95%, more than 96%, more than 97%, more than 98%, more than 99%, or even more than 100% charged when often in an overcharged state. During overcharging, bubbles (such as hydrogen bubbles) are generated in conventional lead-acid batteries, and these circulating bubbles serve to mix the liquid electrolyte (acid) in the battery.

[0010] On the other hand, start / stop vehicles continuously draw power from the battery and thus are in a state of partial charge. During partial charging, no bubbles are generated, internal mixing of the electrolyte is substantially reduced, leading to stratification within the battery. Thus, stratification is a problem in start / stop flooded lead-acid batteries and various enhanced flooded batteries, while stratification was not a problem at all for more conventional or traditional flooded lead-acid batteries operating in an overcharged or fully charged (or near fully charged) state.

[0011] Stratification is a term for the process by which denser sulfuric acid becomes concentrated at the bottom of the battery, resulting in a correspondingly higher concentration of water at the top of the battery. Stratification is undesirable in flooded lead-acid batteries such as enhanced flooded lead-acid batteries or start / stop flooded lead-acid batteries. A decrease in acid level at the top of the electrodes can interfere with the uniformity and charge acceptance within the battery system and can increase the internal resistance variation from the top to the bottom along the height of the battery. An increase in acid level at the bottom of the battery can artificially raise the battery voltage and potentially interfere with the battery management system, which may in some cases send an unintended / false state of health signal to the battery management system. Overall, stratification can cause higher resistance along parts of the battery, leading to electrode problems and / or shortening of battery life. Considering that start / stop batteries and / or other enhanced flooded lead-acid batteries are expected to increasingly proliferate in hybrid and fully electric vehicles that increase fuel efficiency and reduce CO2 emissions of vehicles, it is highly necessary to solve stratification reduction and / or acid mixing improvement.

[0012] In some cases, stratification can be avoided by using valve-regulated lead-acid (VRLA) technology that immobilizes the acid either by a gelled electrolyte and / or an absorbent glass mat (AGM) battery separator system. In contrast to the free-flowing electrolyte within flooded lead-acid batteries, in VRLA AGM batteries, the electrolyte is absorbed in fibrous or fibrous materials such as glass fiber mats, polymer fiber mats, gelled electrolytes, and others. This is the case. However, VRLA AGM battery systems are substantially more costly to manufacture than flooded battery systems. In some cases, VRLA AGM technology can be more sensitive to overcharging, can dry out at high temperatures, can gradually lose capacity, and can have lower specific energy. Similarly, in some cases, gel VRLA technology can have higher internal resistance and can reduce charge acceptance.

[0013] Therefore, there is a need to further develop enhanced flooded lead-acid batteries, such as enhanced flooded start / stop batteries, that do not experience stratification during use and / or exhibit a reduced or significantly reduced level of stratification during use. There is a need for improved enhanced flooded lead-acid batteries that have improved uniformity and performance compared to what was previously available and that have performance that competes with or even exceeds that found in certain VRLA AGM batteries.

[0014] A battery separator is used to separate the positive and negative electrodes or plates of a battery to prevent electrical short circuits. Such battery separators are usually microporous so that ions can pass through the separator between the positive and negative electrodes or plates. The separator can be made of polyolefins such as polyethylene and polypropylene, wood, paper, rubber, PVC, and glass fibers. 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, and in some cases, such a separator may comprise a backweb and a plurality of ribs on one or both sides of the backweb. See Besenhard, J.O., Editor, Handbook of Battery Materials, Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), ch. 9, pp. 245-292. Some separators for automotive batteries are manufactured in long lengths and in rolls and are then folded and sealed along the ends (or specific ends) to form a pouch or envelope or sleeve or pocket that receives the battery electrodes. For example, certain separators for industrial (or traction or deep-cycle storage) batteries are cut to approximately the same size as the electrode plates (small pieces or leaves).

[0015] Separators made from polyolefins such as polyethylene usually contain silica to facilitate wetting of the separator by the hydrophilic electrolyte. In some cases, a hydrophilic material such as a glass mat is attached to the separator to assist wetting and retain the active material coated on the positive electrode.

[0016] The electrodes in lead-acid batteries are often manufactured from lead alloys with a relatively high antimony content. The lead / antimony alloy has advantages both during the manufacturing process of the electrode frame (as an example, improvement of the fluidity of the molten metal in the mold, greater hardness of the cast electrode frame, etc.) and during the use of the battery; especially in the case of cyclic loading, good contact between the terminal and the active material is ensured at the positive electrode in addition to mechanical stability, and as a result, early capacity degradation does not occur (the "antimony-free" effect), providing improved cycle performance. In addition, with respect to deep-cycle batteries, antimony is often present in the positive lattice of the battery.

[0017] However, the positive electrode containing antimony has the disadvantage that antimony can dissolve into ions in the electrolyte and move through the separator. Since antimony is less active than lead, it can form a film on the negative electrode. This process is described as antimony poisoning. Due to the decrease in the overvoltage for hydrogen, antimony poisoning results in an increase in water consumption, and thus the battery requires more maintenance. In particular, antimony can catalyze the decomposition of water, and the water decomposition can consume a part of the energy required for the complete recharge of the battery so that the charging voltage is reduced and the energy required for the complete recharge of the battery is increased. Attempts have already been made to completely or partially replace antimony in lead alloys containing other alloy components, but satisfactory results have not been obtained. Overall, the presence of antimony in the positive lattice of deep-cycle batteries can cause a reduction in cycle life.

[0018] U.S. Patent No. 5,221,587, which is incorporated herein by reference in its entirety, discloses a battery separator including both plastic and rubber. The rubber has been found to slow down the rate of antimony poisoning. U.S. Patent No. 5,221,587 discloses coating the rubber on the sheet or incorporating the rubber into the sheet.

[0019] There remains a need for an improved separator that provides at least for certain applications or batteries, improved cycle life, reduced antimony poisoning, reduced water consumption, reduced float charge current, and / or reduced voltage required to fully charge the battery. More particularly, there remains a need for an improved separator and an improved battery (such as a golf cart or golf cart battery) comprising the improved separator, which provides improved battery life, reduced battery failures, reduced water 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, minimized increase in internal electrical resistance, reduced electrical resistance, improved wettability, reduced electrolyte wetting time, reduced battery formation time, reduced antimony poisoning, reduced stratification, improved acid diffusion, and / or improved uniformity within a lead acid battery.

[0020] In an EFB system, the electrodes are made of a lead alloy. During the manufacture of such an EFB, a paste is applied to the grids and cured to form the electrodes. The paste may include one or more of carbon black, barium sulfate, lignosulfonate, sulfuric acid, and water. The curing method changes the paste into a mixture of lead sulfate that electrochemically becomes the active material during the initial charge of the battery. The paste on the positive electrode is known as the positive active material ("PAM"). Similarly, the active material on the negative electrode is known as the negative active material ("NAM"). During the charge and discharge cycles of the battery, the electrodes expand and contract. Over time, this distortion of the electrodes causes the active material to fall off and physically separate from the electrodes. As the active material increasingly falls off the electrodes, the electrodes become less effective and the battery performance and life are reduced. Thus, there is a need for a new battery separator and / or battery technology that satisfies and overcomes the problems arising from current lead acid battery systems, particularly preventing or retarding the shedding of active material from the electrodes in enhanced flooded batteries. SUMMARY OF THE INVENTION

[0021] The details of one or more embodiments are described in the following specification. Other features, objects, and advantages will become apparent from the specification and the claims. According to at least the selected embodiments, the present disclosure or invention can address the above problems or needs. According to at least certain purposes, aspects, or embodiments, the present disclosure or invention can provide an improved separator and / or battery that overcomes the aforementioned problems, for example, by providing a battery having improved active material retention on the electrodes. In certain embodiments, such improved active material retention is provided by an improved separator comprising an improved retention mat such as an improved PAM retention mat. The specific embodiments disclosed herein are directed to lead-acid battery separators for retaining PAM, but these may also be used for retaining NAM.

[0022] One embodiment of the invention provides a lead-acid battery separator comprising a porous membrane or a web having a plurality of ribs thereon. The ribs may be present on one or both of the positive electrode facing surface and the negative electrode facing surface. The separator of the invention further comprises a fiber mat on the positive electrode facing surface.

[0023] According to at least selected embodiments, aspects or purposes, the present disclosure or invention can be directed to or provide a novel or improved separator, battery separator, liquid battery separator, enhanced liquid battery separator, fiber mat, batteries, cells, and / or methods of manufacturing and / or using such separators, battery separators, fiber mats, enhanced liquid battery separators, cells and / or batteries. According to at least certain embodiments, the present disclosure or invention can be directed to a novel or improved enhanced liquid lead-acid battery separator, fiber mat, liquid battery for deep cycle applications, and / or enhanced liquid battery, and / or system, vehicle, and / or the like, including such separator, mat or battery, and / or improved methods of manufacturing and / or using such improved separator, mat, cell, battery, system, vehicle, and / or the like. According to at least certain embodiments, the present disclosure or invention can be directed to an improved separator for an enhanced liquid battery and / or improved methods of manufacturing and / or using such battery comprising such improved separator. According to at least selected embodiments, the present disclosure or invention can be directed to a separator, liquid battery separator, preferably or particularly a separator for an enhanced liquid battery having low electrical resistance and / or high cold cranking amps. Additionally, methods, systems and battery separators for enhancing battery life, reducing water loss, reducing internal resistance, improving wettability, reducing stratification, improving acid diffusion, improving cold cranking amps and / or at least improving uniformity within an enhanced liquid battery are disclosed herein.According to at least certain embodiments, the present disclosure or invention is directed to an improved separator for a reinforced flooded battery, the separator comprising one or more performance enhancing additives or coatings, an increased porosity, an increased pore volume, amorphous silica, high oil absorption silica, high silanol group silica, retention and / or improved retention of active material on the electrodes, and / or any combination thereof.

[0024] According to at least certain embodiments, the present disclosure or invention is directed to an improved flooded lead acid battery for such a battery, an improved battery separator, mat, composite separator, laminated separator, positive envelope, negative envelope, and / or the like, and / or a method of manufacturing, testing, or using such an improved flooded lead acid battery, or a combination thereof.

[0025] According to at least certain embodiments, aspects, and / or objectives, the present invention, application, or disclosure can provide a solution, a novel product, an improved product, a novel method, and / or an improved method, and / or can address the heart, need, and / or problem of issues such as PAM shedding, NAM shedding, electrode distortion, active material shedding, active material loss, and / or physical separation, electrode efficiency, battery performance, battery life, and / or cycle life, and / or can address the challenges arising from current lead acid batteries or battery systems with a novel battery separator, novel battery technology, and / or novel battery method and / or system, preferably or particularly in a reinforced flooded lead acid battery, PSoC battery, ISS battery, ESS battery, and / or the like, particularly in a reinforced flooded lead acid battery, or other flooded batteries, AGM batteries, partial state of charge (PSoC) batteries, ISS batteries, energy storage system (ESS) batteries, or the like, so as to prevent or delay the shedding of active material from the electrodes of other batteries. A Terry separator, novel battery technology and / or a novel battery method and / or system can be provided.

Brief Description of the Drawings

[0026]

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[0027] Referring to FIGS. 1A and 1B, photographs of exemplary embodiments of the fiber mat are shown. FIGS. 1C and 1D are higher resolution photographs of exemplary embodiments of the fiber mat. The fiber mat may be a nonwoven fabric, a fleece, a mesh, or any combination of these layers. The fiber mat may be a single layer, a two-layer, or other multi-layer mat. An exemplary nonwoven mat may have a thickness in the range of about 100 μm to about 900 μm, preferably in the range of about 200 μm to about 450 μm. FIGS. 1C and 1D show the pattern of the fiber bundles. This can be done during mat formation and the fibers may be collected in specific low locations in the drainage mesh as the fiber dispersion medium ceases to flow. Additionally, the mat may have coma fibers.

[0028] Preferred fiber mat compositions may be, for example, glass, synthetic, or any combination thereof. Exemplary embodiments of the fiber mat may be 5% - 25% synthetic fibers, with the balance being glass and / or binder. However, the mat may be all glass or all synthetic. Such examples of synthetic fibers can be polypropylene, polyesters such as polyethylene terephthalate ("PET"), acrylic resins, other plastics, or any combination thereof. Further, the fiber composition may be a mixture of fibers having polymers, homopolymers, or copolymers, or combinations of these compositions. Whatever the composition of the fiber mat, it is preferably resistant to the acid electrolyte of a lead-acid battery. These materials are rather hydrophobic and thus cause gas entrapment. Thus, surfactant coatings as generally described herein may be added.

[0029] The fiber mat may further have fillers such as particulate silica, which can increase the surface area and decrease the pore size. The fiber mat composition may further have soluble fibers. The fiber mat may contain a gelling agent and can also help resist delamination. Additionally, the fiber mat may generally contain wetting agent additives or coatings as described below herein.

[0030] An exemplary fiber mat may have a preferred air permeability in the range of about 1500 l / m 2 s to about 2500 l / m 2 s.

[0031] An exemplary fiber mat may preferably have an average pore size of about 4.0 μm to less than 5.0 μm (when measured as the effective diameter). The fiber mat pore size is preferably smaller than the particle size of the active material used in the associated electrode. Table 1 below compares the pore sizes in μm of the fiber mat according to the present invention with a conventional glass mat. 2 are being compared.

[0032]

Table 1

[0033] The exemplary fiber mat may have an electrical resistance (“ER”) in the range of about 6 mΩ·cm 2 to about 14 mΩ·cm 2 and 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

[0034] The exemplary fiber mat may have a basis weight or grammage in the range of about 50 g / m 2 to about 100 g / m 2 and in some embodiments, a preferred basis weight or grammage in the range of 50 g / m 2 to about 65 g / m 2

[0035] The exemplary fiber mat may have a preferred binder ratio in the range of about 15 wt% to about 21 wt%.

[0036] The exemplary fiber mat may have a preferred tensile strength in the machine direction (MD) of about 200 N / 50 mm and a preferred tensile strength in the cross machine direction (CMD) of about 150 N / 50 mm.

[0037] Furthermore, the fibers may or may not be hollow, and the cross-sectional shape of the fibers may be round, circular, elliptical, rectangular, kidney bean-shaped, dog bone-shaped, racetrack-shaped, polygonal, or any combination thereof. Additionally, the exemplary fibers may have multiple components in a parallel structure, or a sheath-core structure, or a sea-island structure. Further, the sheath-core structure may be on top of any of the above shapes, and the core may be centered or eccentric.

[0038] ​​Next, referring to FIG. 1E, four low-magnification SEM images taken from two separate positions of the exemplary fiber mat and two separate positions of the conventional glass mat are shown. The images show that the exemplary fiber mat has a fiber web that is packed more densely than the conventional glass mat. Further, the fibers and the open area of the exemplary fiber mat are smaller than those of the conventional glass mat.

[0039] In FIG. 1F, SEM images were obtained from samples taken from two separate positions, and then two separate areas were obtained from each sample position. This was done to avoid any area bias. The images were taken at a higher magnification than in FIG. 1E. These images further show the packing density of the fibers and also show some fiber bundles, which are likely due to the binder used and its binder ratio. The fiber mats useful in various embodiments described herein may include bunches or bundles of fibers such as bunches or bundles of glass fibers and / or synthetic fibers. In certain embodiments, such bunches or bundles may be twisted before the fibers are joined to each other. In such embodiments, twisting may be performed, and a binder may be applied to hold the twist in place. In such embodiments, a separator comprising a fiber mat including bunches or bundles of fibers may exhibit enhanced strength compared to a separator including a conventional mat. Similarly, when the fibers are twisted, such a separator comprising such a fiber mat may exhibit an even more significant enhancement in strength compared to a separator comprising a conventional mat. When manufacturing such fiber mats according to various preferred embodiments defined herein using the wet process, composite fiber bundles may be manufactured, and such composite fiber bundles include glass fibers as well as synthetic polymer fibers, by way of example only, polyester fibers or PET fibers. Fibers are included.

[0040] The exemplary fiber mat may have a synthetic fiber diameter of about 7.2 μm (±0.5 μm) with a confidence limit of ±95%. Table 2 below compares the fiber diameters in μm of the fiber mat according to the present invention with those of the conventional glass mat.

[0041]

Table 2

[0042] In addition, the fiber mat may be manufactured with fibers bundled either before mat formation or while forming the mat. Multiple fibers having different material compositions, different cross-sectional shapes, different fiber diameters, and any combination thereof may be used to comb or twist the bundle. The bundle may be laid in a pattern direction, randomly, or in a combination thereof. The bundled fibers may be laid on and / or within a randomly laid non-woven or fiber mat layer. Thus, the resulting fiber mat may have a wavy surface, a non-wavy surface, or a combination thereof. FIGS. 1C and 1D are photographs of exemplary fiber mats having a wavy surface. The bundle may be formed during mat manufacture. The bundle can be easily formed by a carrier wire or the profile of the surface used in mat manufacture. Further, the mat may be laid in two separate ways. For example, the bundle may be formed with a water-insoluble binder and then a second layer of non-woven fibers may be laid to hold the fibers together. The bundle may be placed on either or both surfaces of the mat.

[0043] FIG. 1G shows an image used to measure the fiber diameter of an exemplary fiber mat when taken across a single fiber at a linear distance, and the fibers in the bundle were not measured, and two diameters of each measured fiber were photographed (if possible). The data of FIG. 1G are shown in Table 1 above. FIG. 1H is an image used to measure the pore size of the fiber mat. The data of FIG. 1H are shown in Table 2 above.

[0044] An exemplary flooded lead-acid battery typically consists of one or more battery cells, each of which in turn typically has one or more positive and negative electrodes. The electrodes may be configured as cast or stamped plates or grids. The electrodes may be configured as cylinders or tubes. Separators are further spaced apart between the respective positive and negative electrodes. In the present disclosure, separators and fiber mats are disposed between each electrode. By way of example, FIG. 2A shows a battery 100 having a single cell, as well as a single negative electrode 102a and a single positive electrode 104a. However, it is understood that a typical lead-acid battery includes multiple electrodes, including a series of alternating positive and negative electrodes. The negative electrode 102a is electrically coupled to a negative battery terminal or post 102b. Similarly, the positive electrode 104a is electrically coupled to a positive battery terminal or post 102c. The positive battery terminal or post 104b is electrically connected to 2B is similar to FIG. 2A, except that it has two negative electrodes 202a. The electrodes 102a, 104a, 202b, 204b are typically lead or lead alloys. Exemplary lead alloys typically contain antimony (Sb), calcium (Ca), tin (Sn), copper (Cu), bismuth (Bi), combinations thereof, and the like.

[0045] Turning now to FIG. 2A, an exemplary flooded lead-acid battery 100 is shown with a single negative electrode 102a and a single positive electrode 104a, each of which is referred to as a negative terminal or a negative electrode, respectively. It is electrically connected to the negative terminal or post 102b and the positive terminal or post 104b, respectively. The terminal parts 102b and 104b are arranged on the outer surface of the battery 100 and usually extend from the upper part of the battery 100. A typical wet lead-acid battery 100 is understood to have three or more electrodes. However, for simplicity, only two are shown in this example. The exemplary battery 100 further includes an electrode 101 and is substantially filled with the electrode 101, and the dotted line indicates the filling line of the electrolyte 101. In the exemplary embodiment, the electrode and separator assembly is substantially submerged in the electrolyte. The electrolyte 101 is usually sulfuric acid (H2SO4) having a specific gravity of about 1.20 to 1.30, preferably about 1.26 to 1.28. It is understood that any preferred range of the specific gravity depends on the use of the battery.

[0046] Staying with FIG. 2A, the exemplary separator assembly is disposed between the electrodes and includes a separator layer 106 (such as a microporous membrane separator layer) and an exemplary fiber mat 108. The separator layer 106 is adjacent to the negative electrode 102a, and the fiber mat 108 is disposed adjacent to the positive electrode 104a. For the purpose of explaining the present invention, the separator layer 106 and the fiber mat 108 may both be collectively referred to as a separator assembly, but it is understood that they may or may not be joined to each other, and may or may not be laminated. The fiber mat 108 may not be joined to any of them, may be joined or fixed to the electrode on the outer surface of the active material, may be incorporated into the paste paper applied to the electrode, or may be pressed against the electrode active material in some way, or any combination of these is possible. Alternatively, the fiber mat 108 may be disposed between the negative electrode 102a and the separator layer 106, and it is further understood that there may be fiber mats on both sides of the separator layer 106. The inventors assume that the fiber mat will prevent or delay the process of dropping or desorbing the pressure material from the adjacent electrode when the active material is PAM or NAM.

[0047] As shown in FIG. 2A, the separator layer 106 and the fiber mat 108 may be provided as leaves laid between the electrodes. The separator layer 106 is preferably larger in lateral and longitudinal dimensions than the electrodes 102a, 104a (i.e., the separator layer 106 is wider and taller than the electrodes 102a, 104a). The fiber mat 108 may extend from the lateral end to the lateral end of the separator layer 106, or from the end rib to the end rib (ribs not shown). Further, the separator layer 106 may simply be flat and have no ribs, or may be embossed.

[0048] Turning now to FIG. 2B, an exemplary flooded lead-acid battery 200 is shown with two negative electrodes 202a and a single positive electrode 204a disposed therebetween, each of which is electrically coupled to a negative terminal portion or negative post 202b and a positive terminal portion or positive post 204b, respectively. A typical flooded lead-acid battery is understood to have four or more electrodes. However, for simplicity, only three are shown in this example. The exemplary flooded lead-acid battery 200 further includes an electrolyte 201, generally as described herein, and is substantially filled with the electrolyte. The dashed line indicates the fill line of the electrolyte 201, and the electrodes and separator assembly are substantially submerged therein.

[0049] Staying with FIG. 2B, an exemplary separator assembly comprising an envelopable separator layer 206 and an envelopable fiber mat 208 is shown enveloping the positive electrode 204a, with the separator layer 206 enveloping the fiber mat 208. The separator layer 206 preferably abuts both negative electrodes 202a, and the fiber mat 208 preferably abuts the positive electrode 204a and is disposed between the separator layer 206 and the positive electrode 204a. The separator layer 206 and the fiber mat 208 may be joined to each other, may not be joined to each other, or may be laminated as one unit, or may not be laminated. The fiber mat 208 may not be joined to either, on the outer surface of the active material It is further understood that it may be joined or fixed to the electrode, or may be incorporated into the paste paper applied to the electrode. Alternatively, it is understood that the fiber mat 208 may be disposed between the negative electrode 202a and the separator layer 206, and the fiber mat 208 may envelope the separator layer 206. Fiber mats may be present on both sides of the separator layer 206. The inventors assume that the fiber mat will prevent or delay the process of dropping or desorbing the pressure substance from the adjacent electrode when the active material is PAM or NAM.

[0050] As described above, an exemplary separator assembly comprising a combination of the separator layer 206 and the fiber mat 208 may be envelopable. The outer surfaces of the combination may be sealed to each other as continuous or intermittent seams. Such sealing means are well known to those skilled in the art. In addition, the bottom fold of the envelope may be closed, and it may have one or more openings having a length shorter than the width of the envelope. The fiber mat 208 may extend from the lateral end to the lateral end of the separator layer 206, or from the end rib to the end rib (the rib is not shown). Further, the separator layer 206 that envelopes may simply be flat and may not have ribs.

[0051] Some other exemplary embodiments of the separator assembly structure include: a negative or positive electrode envelope; a negative or positive electrode sleeve, a negative or positive electrode hybrid envelope (a variant of the standard envelope); both plates can be enveloped or sleeved, and any combination of these can be mentioned. In addition, various separators of the present disclosure may include a separator layer (such as separator layer 106), a fiber mat (such as fiber mat 108), and a glass mat (not shown).

[0052] The fiber mats 108, 208 may be simply arranged adjacent to the separator layers 106, 206, or may be joined, attached, or laminated to the separator layers 106, 206 in some way. Some means of attaching the fiber mats 108, 208 to the separator layers 106, 206 are known to those skilled in the art. Such means can include, for example, bonding the various layers to each other by an adhesive, ultrasonic welding or sealing, or ultrasonic sewing. Preferably, an adhesive such as an acrylate or polyethylene hot melt is used to improve the bond between the microporous polymer layer and the fiber layer. The adhesive is preferably applied between the layers of the separator in the form of individual spots or continuous stripes. When the separator layer 106 and the fiber mat 108 are laminated, the fiber mat provides additional support to the separator layer and thus provides a larger space for the electrolyte, so the rib (not shown) spacing may be further increased compared to the separator layer not laminated with the fiber mat. However, the separator layer 106 and the fiber mat 108 need not be laminated to each other, or alternatively, they may simply be arranged adjacent to each other.

[0053] As the separator of the present invention, preferably, a porous membrane made of a natural or synthetic material such as polyolefin, polyethylene, polypropylene, phenolic resin, natural or synthetic rubber, latex, synthetic wood pulp (SWP), glass fiber, synthetic fiber, cellulose fiber, or a combination thereof (a microporous membrane having pores less than about 1 micron, a mesoporous or macroporous membrane having pores larger than about 1 micron) can be mentioned. More preferably, the separator embodiment includes a microporous membrane made of a thermoplastic polymer. The preferred microporous membrane may have a pore diameter of about 0.1 micron (100 nanometers) and a porosity of about 60%. As the thermoplastic polymer, basically, all acid-resistant thermoplastic materials suitable for the use of lead-acid batteries can be mentioned. Preferred thermoplastic polymers include polyvinyl and polyolefin. Examples of polyvinyl include polyvinyl chloride (PVC). Examples of polyolefin include polyethylene including ultra-high molecular weight polyethylene (UHMWPE), and polypropylene. One preferred embodiment may include UHMWPE and a filler (for example, silica). Generally, the preferred membrane can be manufactured by mixing a thermoplastic polymer such as a filler, UHMWPE, latex and / or rubber (if desired), and a processing plasticizer (for example, process oil) in an extruder.

[0054] Examples of the microporous membrane layer include polyolefins such as polypropylene and ethylene-butene copolymers, preferably polyethylene, more preferably high molecular weight polyethylene (e.g., polyethylene having a molecular weight of at least 600,000), even more preferably ultra-high molecular weight polyethylene (e.g., polyethylene having a molecular weight of at least 1,000,000, particularly more than 4,000,000, most preferably 5,000,000 to 8,000,000 (measured by a viscosity measurement method and calculated by the Margolie formula)), a standard load melt index of substantially zero (measured as defined in ASTM D1238 (Condition E) using a standard load of 2,160 g) and a viscosity number of 600 ml / g or more, preferably 1,000 ml / g or more, more preferably 2,000 ml / g or more, most preferably 3,000 ml / g or more (measured in a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C).

[0055] In certain selected embodiments, a membrane can be produced by compounding about 5 to 15 wt% polymer, optionally about 10 wt% polymer, about 10 to 75 wt% filler, optionally about 30 wt% filler, and about 10 to 85 wt% process oil, optionally about 60 wt% process oil. In other embodiments, the filler content is reduced and the oil content is made higher, for example, greater than about 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt% or 70 wt%. The filler:polymer ratio (by weight) can be approximate (or can be between these specified ranges approximately), for example, 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1 or 6:1. The filler:polymer ratio (by weight) can be from about 1.5:1 to about 6:1, optionally 2:1 to 6:1, about 2:1 to 5:1, about 2:1 to 4:1, optionally about 2:1 to about 3:1. The amounts of filler, oil, polymer (such as polyethylene), and rubber and / or latex (if desired) are all balanced for operability as well as for desired separator properties such as electrical resistance (ER), porosity, physical strength, twist, and others.

[0056] According to at least one embodiment, the porous membrane can include ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil and precipitated silica. According to at least one embodiment, the microporous membrane can include ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil, additives, and precipitated silica. The mixture can also include trace amounts of other additives or reagents common in the field of separator technology (wetting agents, colorants, anti-static agents, and / or the like). In some cases, the microporous polymer layer can be a homogeneous mixture of 80-100% by volume of polyolefin, 0-40% by volume of plasticizer, and 0-92% by volume of inert filler material. The filler can be dried and micronized silica. A preferred plasticizer is petroleum. Since the plasticizer is the component that can be most easily removed from the polymer-filler-plasticizer composition, it is useful for imparting porosity to the battery separator.

[0057] In some embodiments, the porous membrane can be manufactured by mixing, in an extruder, about 30 wt% silica with about 10 wt% UHMWPE and about 60 wt% process oil. Passing the components through a heated extruder, passing the extrudate produced by the extruder through a die and a nip formed by two heated calendar rolls to produce a continuous web, extracting a substantial amount of the process oil from the web using a solvent, drying the extracted web, slitting the web into lanes of a predetermined width, and winding the lanes onto rolls to produce a microporous membrane. The calendar rolls can be engraved with various groove patterns to impart ribs, serrations, embossments, and the like to the membrane. Alternatively, or in addition, ribs and the like can be imparted to the porous membrane by passing the extruded membrane through an additional appropriately engraved calendar or embossing roll or press.

[0058] ​Suitable fillers include silica, alumina, talc, and / or combinations thereof. Silica, which has a relatively high oil absorption and affinity for mineral oil, is desirably dispersible in a mixture of polyolefin (such as polyethylene) and mineral oil when manufacturing lead-acid battery separators of the type shown herein. Additionally, the silica used herein may be precipitated silica and / or amorphous silica. In some selected embodiments, the filler has an average particle size of 25 μm or less, optionally 22 μm or less, 20 μm, 18 μm, 15 μm, or 10 μm. Optionally, the average particle size of the filler particles (such as silica) is 15 - 25 μm. The particle size of the silica filler contributes to the oil absorption of the silica and / or the surface area of the silica filler. The silica particles in the final product or separator can be within the above sizes. However, the initial silica used as a raw material is obtained as one or more agglomerates and / or aggregates and can have a size of about 200 μm or more. In some embodiments, the final separator has a residual oil or final oil content in the range of about 0.5% to about 40% by weight of the separator sheet product, optionally about 10 - about 30% residual process oil, and optionally about 20 - about 30% residual process oil or residual oil. Regarding the pore size of the separator membrane (optionally including polyolefins such as polyethylene, and latex and / or rubber in certain embodiments), the pore size can be 100 μm or less, and in certain embodiments, it can be submicron in the range of about 0.1 - 10 μm. In certain embodiments, the separator membrane can have an average porosity of greater than about 10% and less than about 90%, and in other embodiments, the porosity can be greater than about 40% and less than about 80%. In some selected embodiments, the separator membrane can have a porosity of greater than about 50%, and in other embodiments, the porosity can be greater than about 60%, greater than about 65% in certain embodiments, and greater than about 70% in certain other embodiments. One preferred embodiment provides a porous membrane having a porosity of at least greater than about 64%.

[0059] The microporous membranes produced according to the present invention, which contain polyethylene, a filler (such as silica), and latex and / or rubber, typically have residual oil content; in some embodiments, such residual oil content is about 0.5% to about 40% of the total weight of the separator membrane (in some embodiments, about 10 to 30% of the total weight of the separator membrane, and in some cases, about 20 to 30% of the total amount). In the present specification, in certain selected embodiments, some to all of the residual oil content in the separator may be replaced by the addition of more performance-improving additives, such as surfactants having an HLB of less than 6, or surfactants such as nonionic surfactants. For example, performance-improving additives such as surfactants such as nonionic surfactants may contain residual oil content from an amount of 0.5% or less to the total amount (e.g., up to 20 or 30 or even 40%) of the total weight of the microporous separator membrane, thereby partially or completely replacing the residual oil in the separator membrane.

[0060] The separators disclosed herein contain rubber, which can be latex and / or natural rubber, synthetic rubber, or a mixture thereof. Examples of natural rubber include one or more formulations of polyisoprene that can be purchased from various suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloropene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, norbornene rubber, acrylate rubber, fluororubber, and Examples of rubbers include silicone rubber and copolymer rubbers such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber (EPM and EPDM), and ethylene-vinyl acetate rubber. The rubber may be a crosslinked rubber or an uncrosslinked rubber. In certain preferred embodiments, the rubber is an uncrosslinked rubber. In certain embodiments, the rubber may be a blend of crosslinked and uncrosslinked rubbers. The rubber can be present in the separator in an amount of at least about 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% based on the final separator weight (the weight of the polyolefin separator sheet or the layer containing the rubber and / or latex). In certain embodiments, the rubber can be present in an amount of 1-20 wt%, 2-20 wt%, 2.5-15 wt%, 2.5-12.5 wt%, 2.5-10 wt%, or 5-10 wt%.

[0061] To manufacture the separator according to the present invention, rubber and / or latex may be incorporated into an extruder together with a polymer (e.g., polyethylene), a filler (e.g., silica), and a process oil and / or a plasticizer. In other embodiments, a microporous membrane such as a polyethylene membrane can be coated on one or both sides, preferably the side facing the negative electrode, with a liquid slurry containing rubber and / or latex, silica if necessary, and water, and then dried, and / or a thin film of this material can be formed on the surface of the aforementioned microporous membrane such as a polyethylene membrane. For better wettability of this layer, known wetting agents can be added to the slurry for use in lead-acid batteries. In certain embodiments, the slurry can also contain one or more performance enhancing additives (e.g., surfactants) described in detail below. After drying, the porous layer and / or the thin film are formed on the separator surface and adhere very well to the microporous membrane, increasing the electrical resistance only slightly if at all. After adding rubber to obtain the separator, it can be further pressed using either a press machine or a calender stack or roll. Pressing or calendering can be engraved to impart ribs, grooves, serrated edges, serrated ribs, embosses, and the like to the separator.

[0062] A further embodiment of the present invention relates to forming a rubber film on a membrane by impregnation and drying. For this purpose, a glass mat, fleece or fabric made of synthetic fibers or a mixture with synthetic fibers, such as those described in the fiber mat above, can be used as the carrier material. By way of example, the fiber mat can be a carrier for performance enhancing additives such as antimony suppressing additives, may be impregnated in the fiber mat, may be contained within the fiber mat, or may be coated on one or more surfaces of the fiber mat. In such embodiments, the slurry and / or coating and / or material contained in and / or on the fiber mat may include one or more performance enhancing additives such as rubber and / or latex, silica if necessary, water, and / or various additives described herein, and in surface embodiments, a thin film of the material can be formed on one or more surfaces of the treated fiber mat. Bonding can be effected by compression or adhesion.

[0063] In various embodiments of the present invention, a porous membrane and / or a microporous membrane containing a polyolefin (such as polyethylene), latex and / or rubber, a filler (such as silica), any residual oil and / or plasticizer, and a performance enhancing additive, in the form of a coating (such as a surfactant coating), is laminated to the fiber mat or another layer such as a fiber mat having improved wicking properties and / or improved electrolyte wetting or retention properties. Such fiber mats may have a thickness of at least 100 μm, in some embodiments at least about 250 μm, at least about 400 μm, at least about 500 μm, at least about 600 μm, at least about 1.3 mm, at least about 2 mm, etc. The laminated separator may then be cut into pieces. In certain embodiments, the fiber mat is laminated to the surface of the microporous membrane separator layer provided with ribs. In certain embodiments, it can be supplied in rolls and / or cut pieces for handling and / or asse The advantages of the embly are provided to battery manufacturers including the improved separator described herein. As previously mentioned, the improved separator may be a freestanding separator sheet or layer without the addition of one or more fiber mats or retention mats.

[0064] In some embodiments, rubber and / or latex can be mixed with a polymer, filler, and process oil (and additional additives as needed) and extruded together to obtain a compounded separator. In this way, a homogeneous separator with rubber uniformly dispersed throughout the membrane can be obtained. In some embodiments, the porous membrane can be impregnated with rubber latex and then dried.

[0065] The mixture can also include trace amounts of other additives or reagents common in the separator art (surfactants, wetting agents, colorants, antistatic agents, antioxidants, and / or the like). The mixture is extruded into the shape of a flat sheet or a sheet with ribs or other protrusions on one or both sides of the sheet. After extruding the membrane, it can be further pressed using either a press machine or a calender stack or roll.

[0066] The press or calendar may be engraved to impart ribs and / or the like to the microporous membrane. The ribs may be in a uniform set, alternating sets, or separated intermittent ribs that are unbroken, continuous, discontinuous, inclined, straight, longitudinal ribs extending substantially in the longitudinal direction ("MD") of the separator (i.e., from the top to the bottom of the separator in the battery), transverse ribs extending substantially in the width direction ("CMD") of the separator (i.e., the lateral direction of the separator in the battery, perpendicular to the MD), cross ribs extending substantially in the width direction of the separator, separated toothed or toothed ribs, serrated edges, serrated ribs, battlements or solid or intermittent zigzag arranged curved or folded battlemented ribs, grooves, channels, textured regions, embossments, depressions, porous, non-porous mini ribs or cross mini ribs, and / or the like, and combinations thereof. Further, any set of ribs may extend from the positive side, negative side, or both sides, or extend to the positive side, negative side, or both sides.

[0067] In some embodiments, the separator membrane can comprise a backweb of at least about 50 μm, at least about 75 μm, at least about 100 μm, at least about 125 μm, at least about 150 μm, at least about 175 μm, at least about 200 μm, at least about 225 μm, at least about 250 μm, at least about 275 μm, at least about 300 μm, at least about 325 μm, at least about 350 μm, at least about 375 μm, at least about 400 μm, at least about 425 μm, at least about 450 μm, at least about 475 μm, or at least about 500 μm (although in certain embodiments, it provides a very thin flat sheet less than 50 μm thick, e.g., 10 μm to 50 μm thick). In certain embodiments, the porous membrane can comprise a backweb of about 50 μm to 1,000 μm, about 50 μm to 750 μm, about 100 μm to 750 μm, about 200 μm to 750 μm, about 200 μm to 500 μm, about 150 μm to 500 μm, about 250 μm to 500 μm, about 250 μm to 400 μm, or about 250 μm to 350 μm.

[0068] In various possible preferred embodiments, the porous membrane includes ribs such as serrated ribs, intercostal ribs, inclined ribs, or intermittent ribs, or combinations thereof. Preferred ribs can be 8 μm to 1 mm in height and can be spaced 1 μm to 20 mm apart. Further, the preferred thickness of the backweb of the microporous polyolefin separator layer (excluding ribs or embossments) can be about 0.05 mm to about 0.50 mm (e.g., about 0.25 mm in certain embodiments). For example, the ribs can be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, 2.0 mm, It can be separated by 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. In some embodiments, the ribs may be in a pattern such that they are at 0° to 90° relative to each other on one side of the separator or on both sides of the polyolefin separator. In some embodiments, the acid mixing ribs may be front ribs, positive electrode side ribs, or positive electrode side surface ribs. Various patterns including ribs on both sides of the separator or the separator layer include positive electrode side ribs and negative electrode side vertical ribs or cross ribs on the second side or back surface of the separator, for example, smaller and denser negative electrode side vertical ribs or cross ribs or mini ribs. In some cases, such negative electrode side vertical ribs or cross ribs may be about 0.025 mm to about 0.1 mm in height, preferably about 0.075 mm in height, but may be the same size as 0.25 mm. Other patterns include ribs on both sides of the separator layer with negative mini ribs on the second side or back surface of the separator (mini ribs extending in the same direction as the width direction compared to the main ribs on the other side of the separator). In some cases, such negative mini ribs may be about 0.025 mm to about 0.25 mm in height, preferably about 0.050 mm to about 0.125 mm in height.

[0069] In certain preferred embodiments, the ribs may be serrated. The serrated edge or serrated ribs may have an average tip length of about 0.05 mm to about 1 mm. For example, the average tip length may be 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or 1.0 mm or less, 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.

[0070] The serrated edge or serrated rib may have an average base length of about 0.05 mm to about 1 mm. For example, the average base length may be about 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or about 1.0 mm or less, 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.

[0071] When a serrated edge or serrated rib is present, it may have an average height of about 0.05 mm to about 4 mm. For example, the average height may be about 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or about 1.0 mm or less, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm. For embodiments where the serrated edge height is the same as the rib height, the serrated rib may be referred to as a protrusion. Such ranges may be applicable to separators for industrial traction type start / stop batteries, and the total thickness of the separator may typically be about 1 mm to about 4 mm, and in automotive start / stop batteries, the total thickness of the separator may be slightly thinner (e.g., typically about 0.3 mm to about 1 mm).

[0072] The serrated edge or serrated rib can have an average center-to-center pitch of about 0.1 mm to about 50 mm. For example, the average center-to-center pitch may be about 0.2 mm or more, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm; and / or about 1.5 mm or less, 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.

[0073] The serrated edge or serrated rib can have an average height ratio to the base width of from about 0.1:1 to about 500:1. For example, the average height ratio to the base width can be about 0.1:1 or more, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300: 1, 350:1, or 450:1; and about 500:1 or less, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, or 25:1.

[0074] The serrated edge or serrated rib can have an average base width ratio to the tip width of from about 1000:1 to about 0.1:1. For example, the average base width ratio to the tip width can be about 0.1:1, 1:1 or more, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1, and / or about 1000:1 or less, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1.

[0075] In some embodiments, the separator can be a depression. The depression is typically a protruding formation or bump on one or more surfaces of the separator. The thickness of the depression can be 1% to 99% of the thickness of the separator. For example, the average thickness of the depression can be less than about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% of the separator. The depressions can be arranged in rows along the separator. The rows or columns can be spaced apart by about 1 μm to about 10 mm. For example, the columns can be spaced apart by 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 10 mm. Conversely, the depressions can be arranged in a random array or randomly.

[0076] The depression can have an average depression length of about 0.05 mm to about 1 mm. For example, the average depression length can be about 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or about 1.0 mm or less, 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.

[0077] The depression can have an average depression width of about 0.01 mm to about 1.0 mm. For example, the average depression width can be about 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or about 1.0 mm or less, 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.

[0078] The depressions can have an average center-to-center pitch of from about 0.10 mm to about 50 mm. For example, the average center-to-center pitch can be about 0.2 mm or more, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm; and / or about 1.5 mm or less, 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.

[0079] The depressions can be of a quadrilateral shape, such as a square and a rectangle. The depressions can have an average depression length ratio to the depression width of from about 0.1: 1 to about 100:1. For example, the average depression length ratio to the depression width can be about 0.1:1, 1:1 or more, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1; and / or about 1000:1 or less, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1.

[0080] In some embodiments, the depressions can be substantially circular. The circular depressions can have a diameter of from about 0.05 to about 1.0 mm. For example, the average depression diameter can be about 0.05 mm or more, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or about 1.0 mm or less, 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.

[0081] Various other shapes related to the recess can similarly be provided. As just one example, such a recess can be triangular, pentagonal, hexagonal, heptagonal, octagonal, oval, elliptical, and combinations thereof.

[0082] In some embodiments, the separator can be characterized by ribs, serrated edges or serrated ribs, recesses, or combinations of these. For example, the separator can have a first series of serrated ribs extending from top to bottom along the separator, and a second series of serrated ribs extending horizontally along the separator. In other embodiments, the separator can have alternately arranged serrated ribs, recesses, continuous, intermittent, or intermittent solid ribs, or combinations of these.

[0083] Table 3 describes some specific embodiments of separators having various parameters that can be used, by way of example and not limitation, to manufacture separators that have serrated edges and / or recesses and prevent stratification and promote acid mixing in a flooded lead-acid battery (sometimes called a enhanced flooded battery).

[0084]

Table 3

[0085] Certain uses for various embodiments experience start / stop cycles such as those utilized in vehicles. This represents the fact that vehicles, and their associated batteries, are operated with intermittent periods of stoppage and thus, efficiently agitate the battery. The separators disclosed herein preferably provide enhanced electrolyte mixing and / or acid circulation as compared to conventional separators. In certain embodiments, the separator provides less stratification when measured by electrolyte density at the top and bottom of the cell. The density difference may be less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, or 1% after the cell has undergone 30, 60, 90 or more start / stop events or cycles. In certain selected embodiments, the density difference may be less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, or 1% after the cell has remained stationary for 24, 48, 72 or more hours.

[0086] Referring now to FIGS. 3A - 3F, some exemplary embodiments show an intermittent rib arrangement in variables that define various intermittent rib patterns for various battery separator embodiments. FIGS. 4A - 4G show a battery separator having intermittent ribs according to an exemplary embodiment of the present disclosure and as defined in the pattern or arrangement of FIGS. 3A - 3F. Exemplary battery separators are shown in FIGS. 4A - 4G; in addition, the exemplary battery separators disclosed herein may have any number of columns 406 1 ~406 n such as column 406.

[0087] Figure 5A details a separator having three zones of a variable intermittent rib pattern with zones that vary horizontally along the width direction of the separator. Note that the zones may extend in the longitudinal direction of the separator or both the longitudinal and width directions of the separator. It is further understood that any number of zones may be present in either or both directions. Additionally, to obtain even better results, the ends of the separator itself may be zones, using different designs and / or rib patterns and / or intermittent rib patterns, etc. to optimize the ends. In certain preferred embodiments herein, separator zones (for multi-zone separators) are formed such that the mass of the patterning in each zone is relatively constant, and / or the patterned separator operates well on battery manufacturing equipment, and / or battery manufacturing is faster due to the effectiveness of acid filling. The ends of the separator itself may be zones of themselves, to optimize the ends using different designs and / or rib patterns and / or intermittent rib patterns, etc. In certain preferred embodiments herein, separator zones (for multi-zone separators) are formed such that the mass of the patterning in each zone is relatively constant, and / or the patterned separator operates well on battery manufacturing equipment, and / or battery manufacturing is faster due to the effectiveness of acid filling.

[0088] Figure 5B shows intermittent rib pattern variables for a zone separator. The subscripted numbers "1" and "2" relate to two different intermittent rib patterns. In a particular embodiment, zones 1 and 3 (subscripted "1") combine the same pattern, such as an intermittent rib pattern, with zone 2 (subscripted "2") having a pattern such as an intermittent rib pattern that varies from zones 1 and 3. Figure 5C shows intermittent rib variables for a single-zone intermittent rib separator.

[0089] Figures 6A - 6H show variations of a zone or multi-zone or three-zone intermittent rib pattern separator.

[0090] Figure 7 shows an exemplary spacer 700 of the present invention having a pattern of intermittent ribs 702 that may be disposed between a separator and an electrode. As shown in the figure, the intermittent ribs 702 are held in place by a network of thin stringers 704. The stringers 704 are shown in a vertical and horizontal arrangement, but it is understood that other angles may be incorporated.

[0091] Figures 8 and 9 illustrate profile prototypes of exemplary acid mixing profiles for various separator layers used herein.

[0092] The separator may comprise a negative electrode side vertical rib or cross rib or mini rib, such as a negative electrode side rib having a height of about 25 to 250 microns, preferably about 50 to 125 microns, more preferably about 75 microns.

[0093] In certain embodiments, the protrusions can include ribs, and each rib has a vertical axis disposed at an angle from 0° to less than 180° with respect to the upper end of the separator. In some cases, all ribs in the separator can be arranged at the same angle, and in other embodiments, ribs arranged at different angles can also exist. For example, in some embodiments, the separator can comprise rows of ribs, and at least a portion of the rows can have ribs at an angle θ with respect to the upper end of the separator. In other examples, one row can have ribs at different angles, but all ribs in one row can have the same approximate angle.

[0094] In certain cases, the entire surface of the separator will comprise rows of protrusions or intermittent ribs, while in other embodiments, certain segments of the separator surface will have neither protrusions nor intermittent ribs. These segments can occur along any edge of the separator, including the upper, bottom, or side, or can occur towards the central portion of the separator, and the segments are surrounded on one or more sides by portions having protrusions.

[0095] Figure 8 depicts a separator 800 comprising an upper end portion 803, as well as a first set of rows R1 and a second set of rows R2. In certain embodiments, the ribs 801 of the first row R1 are arranged at an angle θ1 from 0° to less than 180°, and the ribs 802 of the second row R2 are arranged at an angle θ2 from 0° to less than 180°, which may be different from the angle of the first set of ribs 801 of row R1. It is shown. Although not shown, the angles θ1 and θ2 can further vary over the entire respective rows R1 and R2 of each individual rib 801, 802. In addition, the set of intermittent ribs can be easily patterned by columns.

[0096] FIG. 9 depicts a diagram of a separator 900 having an upper end portion 901 with a central first portion 902 and an outer second portion 903. In a particular embodiment, the central first portion 902 may include one or more sets of rows. As shown in FIG. 9, the first row R1 and the second row R2 are similarly patterned as shown in FIG. 8, the ribs of the first row R1 are arranged at an angle from 0° to less than 180°, and the ribs of the second row R2 may be the same or different from the angle of the ribs of the first row R1 and are arranged at an angle from 0° to less than 180°.

[0097] Staying with FIG. 9, the outer second portion 903 may include a third set of rows R3 having ribs at an angle θ3 with respect to the upper end portion of the back web where θ3 is 0° to 90°, 30° to 85°, 45 ° to 85°, 60° to 85°, 60° to 80°, or 60° to 75°. One preferred value of θ3 is 90°. The outer second portion 903 may include a fourth set of rows R4 having ribs at an angle θ4 with respect to the upper end portion of the back web, where θ4 is from 90° to less than 180°, 95° to 150°, 95° to 120°, 100° to 120°, or 105° to 120°. One preferred value of θ4 is 90°. The ribs of different rows can have the same or different dimensions, and the ribs may be the same or different within a row. The distance between adjacent rows can be from -5 mm to +5 mm, and a negative number indicates the degree of overlap of the rows. The distance can be measured from the central rib to the central rib.

[0098] ​If different rows are present, the rows may be present in a repeating pattern. The simplest repeating pattern -R3-R4- can be seen at separator 900. Other patterns include -R3-R3-R4-; -R3-R3-R3-R4-; -R3-R3-R4-R4-; -R3-R3-R3-R3-R4-; -R4-R3-R3-R3-R4-; -R3-R3-R3-R4-R4-; and the like. In addition, sets of intermittent ribs can be easily patterned by columns.

[0099] In some selected embodiments, the porous separator can have, as protrusions, longitudinal ribs or cross ribs on the negative electrode side on the opposing surfaces of the membrane. The negative electrode side or back ribs may be parallel to the upper end of the separator or may be arranged at an angle with respect to the upper end. For example, the cross ribs can be oriented at about 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15°, or 5° with respect to the upper end. The cross ribs can be oriented at about 90 - 60°, 60 - 30°, 60 - 45°, 45 - 30°, or 30 - 0° with respect to the upper end. Typically, the cross ribs are present on the surface of the membrane facing the negative electrode. In some embodiments of the present invention, the ribbed membrane can have a transverse cross 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, or 1.0 mm. In some embodiments of the present invention, the ribbed membrane can have a transverse cross rib height of 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm or less.

[0100] In some embodiments of the present invention, the ribbed membrane can have a transverse cross rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the present invention, the ribbed membrane can have a transverse cross rib width of 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm or less.

[0101] In certain selected embodiments, the porous membrane can have a transverse cross rib height of about 0.10 - 0.15 mm and a longitudinal rib height of about 0.10 - 0.15 mm. In some embodiments, the porous membrane can have a transverse cross rib height of about 0.10 - 0.125 mm and a longitudinal rib height of about 0.10 - 0.125 mm.

[0102] The microporous membrane can have a backweb thickness of at least 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. The ribbed membrane can have a backweb thickness of about 1.0 mm or less, 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. In some embodiments, the microporous membrane can have a backweb thickness of about 0.1 - 1.0 mm, 0.1 - 0.8 mm, 0.1 - 0.5 mm, 0.1 - 0.5 mm, 0.1 - 0.4 mm, 0.1 - 0.3 mm. In some embodiments, the microporous membrane can have a backweb thickness of about 0.2 mm.

[0103] FIG. 10 shows a side profile of a separator 1000 comprising intermittent ribs 1004 extending outward from the surface of a porous membrane 1002 having a tapered longitudinal end 1006 specified by an angle θ.

[0104] Referring to FIG. 13A, an exemplary battery cell 1300 shows a top-down view of an exemplary battery (the entire battery is not shown). The battery cell includes an acidic electrolyte 1301 such as sulfuric acid (H2SO4) electrolyte that immerses a negative electrode 1302, a positive electrode 1304, and a separator assembly 1308 disposed between the electrodes 1302 and 1304. The separator assembly 1306 may include a porous membrane 1308 and a fiber mat 1310. The porous membrane 1308 may include a series of positive ribs 1308a that contact and extend from the fiber mat 1310. The fiber mat 1310 may closely contact the positive electrode 1304. Although not shown, the porous membrane 1308 may further include negative-side ribs in contact with the negative electrode 1302 as described herein. The negative electrode 1302 may include a negative active material ("NAM"), and the positive electrode 1304 may include a positive active material ("PAM").

[0105] In certain batteries, it is believed that the NAM can expand until sufficient pressure is applied on the porous membrane 1308 to cause it to flex between the positive ribs 1308a. FIG. 13B schematically shows this expansion, and the flexing causes and affects the porous membrane 1308 to contact the fiber mat 1310. When the porous membrane 1308 flexes sufficiently, both the negative electrode 1302 and the positive electrode 1304 become electrolyte-deficient (i.e., acid-starved). This acid starvation can have an adverse effect on battery performance and may be seen in deep-cycle batteries and those operating in PSoC. Although not shown, the porous membrane 1308 may further include negative-side ribs in contact with the negative electrode 1302 as described herein.

[0106] Referring to FIG. 13C, a schematic diagram of an exemplary separator assembly 1306 of the present invention is shown. In this embodiment, an array of positive side ribs 1308a is provided extending from the porous membrane 1308 in a longitudinal direction in contact with the fiber mat 1310. In addition, an array of negative side ribs 1308b is provided extending from the porous membrane 1308 in a longitudinal direction in contact with the negative electrode 1302. This provides space between the NAM and the backweb so that expansion of the NAM does not affect the porous membrane 1308. Additionally, both the positive side ribs 1308a and the negative side ribs 1308b are spaced more closely than those in FIG. 13B to provide more support for the NAM.

[0107] It should be noted that Figures 13A to 13C are not drawn to scale.

[0108] Referring to FIG. 14, an exemplary porous membrane separator 1400 has a positive electrode side rib extending therefrom. The separator includes a backweb 1402 having positive ribs 1404 aligned substantially in the machine direction ("MD") of the separator that is intended to contact a fiber mat (not shown in FIG. 14) in an exemplary battery. The separator includes positive ribs 1410 aligned substantially in the machine direction of the separator and substantially parallel to the positive ribs 1404. The negative ribs 1410 are intended to contact the negative electrode in an exemplary battery. The negative ribs 1410 in this illustrated embodiment are aligned substantially in the machine direction of the separator, although they may alternatively be aligned across the width, commonly known as negative cross ribs.

[0109] Continuing with reference to FIG. 14, a selected embodiment of the separator of the present invention comprises an array of anode-side ribs 1404. The anode-side ribs 1404 comprise a base portion 1406 that may extend the separator length in the longitudinal direction. Then, spaced, tooth-like intermittent peaks, or other protrusions 1408, may extend from the surface of the base portion 1406 such that the teeth 1408 are above the support structure surface of the porous membrane backweb 1402. Further, the base portion 1406 may be wider than the teeth 1408 themselves. The anode-side ribs 1404 are arranged substantially parallel to each other with a typical spacing of from about 2.5 mm to about 6.0 mm, and the typical spacing is about 3.5 mm. The height of the anode-side ribs 1404 (including the base portion 1406 and the teeth 1408) when measured from the surface of the porous membrane backweb 1402 is from about 10 μm to about 4.0 mm, and the typical height is about 0.5 mm. The exemplary rib teeth 1408 of adjacent ribs 1404 may be substantially aligned with each other. However, as illustrated in FIG. 14, the exemplary teeth 1408 may be offset relative to each other from one rib 1404 to an adjacent rib 1404, either completely or partially out of phase with the adjacent rib's phase. As shown in the figure, the teeth 1408 are completely out of phase from the phase of one rib 1404 to the adjacent rib. The anode-side rib teeth 1408 may be spaced at a separator longitudinal pitch of from about 3.0 mm to about 6.0 mm, and the typical spacing is about 4.5 mm.

[0110] As shown in FIG. 14, the cathode-side ribs are shown to be substantially parallel to the longitudinal direction of the separator. However, alternatively, these may be substantially parallel to the width direction. The exemplary cathode-side ribs shown are not hollow and are seen to be substantially straight. However, alternatively, these may be toothed in generally the same manner as the anode-side ribs shown in FIG. 14. The cathode-side ribs may be spaced at a pitch of from about 10 μm to about 10.0 mm, preferably from about 700 μm to about 800 μm, more preferably usually about 740 μm. The height of the cathode-side ribs when measured from the surface of the backweb may be from about 10 μm to about 2.0 mm.

[0111] Alternatively, the positive electrode side ribs may instead be disposed in the exemplary battery such that they contact the negative electrode. Similarly, the negative electrode side ribs may be disposed in the exemplary battery such that they contact the positive electrode.

[0112] Table 4 below details the number of ribs and the percentage of surface contact area for four separators (one exemplary separator of the present invention and three control separators) that are 162 mm × 162 mm (262 cm 2 ). As shown in the figure, the exemplary separator of the present invention comprises ribs with 43 teeth uniformly spaced across the separator width in the width direction. The teeth of the positive electrode side ribs of the exemplary separator of the present invention contact 3. 8% of the 262 cm 2 of the positive electrode. Details of the control separators are shown in more detail in Table 4. Control separators #1, #2, and #3 are understood to be typical of commercially available separators currently used in liquid lead-acid batteries generally available on the market today.

[0113]

[0114] As described above, the inventors have found that by maximizing the number of contact points while simultaneously minimizing the contact area, the goal of enhancing separator resilience can be achieved while maintaining the electrical resistance under control. Furthermore, the toothed design helps to facilitate acid mixing by taking advantage of the movement the battery may undergo. The teeth of the separator ribs may be spaced from about 2.5 mm to about 6.0 mm from the nearest adjacent tooth. The inventors have found that a preferred non-limiting distance is about 4.2 mm between adjacent teeth. Additionally, teeth offset from adjacent rows that are completely out of phase help to facilitate acid mixing. The inventors have also found that the base portion helps to reinforce the backweb sufficient to provide resilience against swelling of the NAM.​​

[0115] Although the exemplary ribs of the present invention are shown and described as being the anode-side ribs, nevertheless these may be provided on the cathode side of the separator, and the illustrated and described cathode-side ribs may be provided on the anode side of the separator.

[0116] In addition, the anode-side or cathode-side ribs may be in any form or combination defined by a solid rib, a separated intermittent rib, a continuous rib, an intermittent rib, an inclined rib, a straight rib, a longitudinal rib extending substantially longitudinally of the porous membrane, a transverse rib extending substantially in the width direction of the porous membrane, a transverse rib extending substantially in the width direction of the separator, a separated rib, a toothed rib, a serrated edge, a serrated rib, a narrow rib or narrow-rib-like rib, a curved rib, a continuously arranged zigzag serrated, a folded intermittent zigzag serrated folded rib, a groove, a channel, a textured region, an emboss, a depression, a column, a mini-column, porous, non-porous, a mini-rib, a cross mini-rib, and combinations thereof.

[0117] In addition, the anode-side or cathode-side ribs may be in any form or combination defined by an angle that is neither parallel nor perpendicular to the end of the separator. Further, this angle may vary across the teeth or rows of the rib. The inclined rib pattern may be a preferred Daramic® RipTide® acid blend rib that can help reduce or eliminate stratification in certain batteries. Further, the angle is with respect to the longitudinal direction of the porous membrane and may be defined as being greater than approximately zero degrees (0°) and less than approximately 180 degrees (180°), and greater than approximately 180 degrees (180°) and less than approximately 360 degrees (360°).

[0118] The ribs may extend uniformly across the width of the separator from side end to side end. This is known as a universal profile. Alternatively, the separator may comprise side panels adjacent to side ends having minor ribs disposed on the side panels. These minor ribs may be disposed more closely and may be smaller. For example, the minor ribs may be 25% to 50% of the height of the primary ribs. The side panels may alternatively be flat. The side panels may provide assistance in sealing the end of the separator to the other end of the separator as discussed below in this specification when enveloping the separator.

[0119] In some selected exemplary embodiments, at least a portion of the negative-side ribs may preferably have a height of about 5% to about 100% of the height of the positive-side ribs. In some exemplary embodiments, the negative-side rib height may be about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95%, or 100% compared to the positive-side rib height. In other exemplary embodiments, the negative-side rib height may be about 100% or less, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% compared to the positive-side rib height.

[0120] In some selected embodiments, at least a portion of the porous membrane may comprise negative-side ribs that are longitudinal or transverse ribs or cross ribs. The negative-side ribs may be parallel to the upper end of the separator or may be disposed at an angle to the upper end. For example, the negative-side ribs may be oriented at about 0°, 5°, 15°, 25°, 30°, 45°, 60°, 70°, 80°, or 90° to the upper end. The cross ribs may be oriented at about 0° to about 30°, about 30° to about 45°, about 45° to about 60°, about 30° to about 60°, about 30° to about 90°, or about 60° to about 90° to the upper end.

[0121] Certain exemplary embodiments may have a base portion. If present, it may have an average base height of about 5 μm to about 200 μm. For example, the average base height may be about 5 μm or more, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, or 200 μm. Further, if present, it may have an average base width that is about 0.0 μm to about 50 μm wider than the tooth width. For example, the average base width may be about 0.0 μm or more, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm wider than the tooth width.

[0122] Certain exemplary embodiments may have teeth or ribbed teeth. If present, they may have an average tip length of about 50 μm to about 1.0 mm. For example, the average tip length may be about 50 μm or more, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be 1.0 mm or less, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0123] At least a portion of the teeth or ribbed teeth may have an average tooth base length of about 50 μm to about 1.0 mm. For example, the average tooth base length may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be about 1.0 mm or less, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0124] At least a portion of the teeth or ribs with teeth may have an average height (the sum of the base portion height and the tooth height) of about 50 μm to about 1.0 mm. For example, the average height may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, these may be about 1.0 mm or less, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0125] At least a portion of the teeth or ribs with teeth may have an average center-to-center pitch within a vertical row of about 100 μm to about 50 mm For example, the average center-to-center pitch may be a value increased in the same way from about 50 μm or more, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm, and up to 50 mm. Alternatively, these may be a value increased in the same way from about 50 μm or less, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm, and up to 50 mm. In addition, adjacent rows of teeth or ribs with teeth may be arranged in the same vertical position or in an offset position. In an offset configuration, adjacent teeth or ribs with teeth are arranged at different vertical positions.

[0126] At least a portion of the teeth or ribs with teeth may have an average height ratio to the base width of about 0.1:1.0 to about 500:1.0. For example, the average height ratio to the base width may be about 0.1:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1, 450:1.0, or 500:1.0. Alternatively, the average height ratio to the base width may be about 500:1.0 or less, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, or 0.1:1.0.

[0127] At least a portion of the tooth or toothed rib can have an average base width to tip width ratio of from about 1,000:1.0 to about 0.1:1.0. For example, the average base width to tip width ratio can be about 0.1:1.0, 1.0:1.0, 2:1.0, 3:1.0, 4:1.0, 5:1.0, 6:1.0, 7:1.0, 8:1.0, 9:1.0, 10:1.0, 15:1.0, 20:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1.0, 450:1.0, 500:1.0, 550:1.0, 600:1.0, 650:1.0, 700:1.0, 750:1.0, 800:1.0, 850:1.0, 900:1.0, 950:1.0, or 1,000:1.0. Alternatively, the average base width to tip width ratio can be about 1,000:1.0 or less, 950:1.0, 900:1.0, 850:1.0, 800:1.0, 750:1.0, 700:1.0, 650:1.0, 600:1.0, 550:1.0, 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, 20:1.0, 15:1.0, 10:1.0, 9:1.0, 8:1.0, 7:1.0, 6:1.0, 5:1.0, 4:1.0, 3:1.0, 2:1.0, 1.0:1.0, or 0.1:1.0.

[0128] Any of the rib patterns described herein may have a spacing between columns to allow for the generation of gas during an overcharge event. Further, the intermittent rib pattern may not have a spacing in the vertical direction between rows of intermittent ribs and may provide strength when folding the separator to form an envelope. Additionally, the intermittent rib separator may be further embossed. It is further understood that any of the rib patterns or other protrusions may be disposed on the inner surface of the battery case or on any or both of the surfaces of the positive and negative electrodes. For batteries disposed in vehicles, a preferred embodiment may dispose the separator in a direction generally parallel to the movement of the vehicle to utilize the start and stop operations of the vehicle.

[0129] Improved separators described herein, such as the intermittent rib separators described herein, can help prevent the formation of sulfation crystals and may also help provide a more uniform heat distribution and / or heat mixing and / or heat dissipation (dissipating heat in a shorter time compared to known separators such as separators with solid ribs for flooded lead-acid batteries) across the separator or the entire separator. The exemplary intermittent rib separators described herein may provide improved or faster or more efficient filling of flooded lead-acid batteries, gel batteries, AGM batteries, PSoC batteries, ISS batteries, and / or enhanced flooded batteries.

[0130] In various embodiments of the present disclosure, the disclosed separator provides for reduced stratification, or even complete elimination of stratification, such that the mixing level or volume uniformity of the acid or electrolyte within the flooded lead battery is 1.0 or nearly 1.0. In various embodiments, the separator disclosed herein is a low electrical resistance (ER) separator. In such embodiments, the separator may include improvements such as an improved filler that increases the porosity, pore size, internal pore surface area, wettability, and / or surface area of the separator. In some embodiments, the improved filler has a higher-order structure and / or a reduced particle size and / or a different amount of silanol groups than known fillers and / or more hydroxylation than known fillers. The improved filler may be able to take up a greater amount of process oil during separator formation without shrinking or compressing when removing the oil after extrusion and / or be more oil absorbent. By way of example, the improved separator may be manufactured using silica having an oil absorption capacity of about 175 to 350 ml / 100 g, in some embodiments 200 to 350 ml / 100 g, in some embodiments 250 to 350 ml / 100 g, and in some further embodiments 260 to 320 ml / 100 g, although other oil absorption capacities are possible as well.

[0131] The filler(s) may further reduce the so-called hydration layer of electrolyte ions that facilitate their transport across the membrane, thereby reducing the overall electrical resistance or ER of the battery, such as a reinforced flooded battery or system.

[0132] The filler(s) may include various species (such as polar species like metals) that promote the flow of electrolyte and ions across the separator. Since such a separator is used in a flooded battery such as a reinforced flooded battery, it reduces the overall electrical resistance.

[0133] The low-ER microporous separator in this specification may further include a novel and improved pore structure and / or a novel and improved fibril structure such that when such a separator is used in such a flooded lead-acid battery, the separator contributes to significantly reducing the electrical resistance in the flooded lead-acid battery. Such an improved pore structure and / or fibril structure can result in a separator where the pores and / or fibrils approximate a shish-kebab (or shish-kabob) structure. Another way to describe the novel and improved pore shape and structure is a texture fibril structure where silica bonding points or points of silica are present in a kebab structure formation on polymer fibrils (the fibrils may sometimes be called shish) within the battery separator. Additionally, 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 a vertebral structure or a spinal cord structure, but the silica bonding points on the polymer kebab structure along the polymer fibrils may sometimes appear like vertebrae or discs ("kebabs") and are sometimes oriented substantially perpendicular to an elongated central spine or fibril (extended chain polymer crystal) approximating a spinal column-like shape ("shish").

[0134] In some cases, an improved battery comprising an improved separator having an improved pore structure and / or fibril structure may exhibit an electrical resistance that is 20% lower, in some embodiments 25% lower, and in some embodiments 30% lower. In some cases, it may even exceed 30% in terms of electrical resistance ("ER"), and such a separator maintains and sustains the balance of other major desired mechanical properties of lead-acid battery separators. Further, in certain embodiments, the separators described herein are novel and / or such that more electrolyte flows through or fills the pores and / or voids compared to known separators has an improved pore shape. The ultra-high molecular weight polyethylene in the separator may include a polymer in a shish-kebab structure formation including a plurality of extended chain crystals (shish structure formation) and a plurality of folded chain crystals (kebab structure formation), and the average repetition or period of the kebab structure formation is from 1 nm to 150 nm, preferably from 10 nm to 120 nm, more preferably from 20 nm to 100 nm (at least in the rib side portion of the separator). In some of these low-ER embodiments of the present separator, the lead-acid battery separator described herein includes a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica; 29 The molar ratio of the OH group to the Si group in the filler measured by Si-NMR is in the range of 21:100 to 35:100, in some embodiments from 23:100 to 31:100, in some embodiments from 25:100 to 29:100, and in certain preferred embodiments in the range of 27:100 or more.

[0135] In certain selected embodiments, the disclosed separator exhibits a reduction in electrical resistance, for example, about 200 mΩ·cm 2 or less, 180 mΩ·cm 2 or less, 160 mΩ·cm 2 or less, 140 mΩ· cm 2 or less, 120 mΩ·cm 2 or less, 100 mΩ·cm 2 or less, 80 mΩ·cm 2 or less, 60 mΩ·cm 2 or 50 mΩ·cm 2 or less, 40 mΩ·cm 2 or less, 30 mΩ·cm 2 or even 20 mΩ·cm 2 of electrical resistance. In various embodiments, the separator described herein exhibits an ER reduction of about 20% or more compared to a known separator of the same thickness. For example, a known separator may have an ER value of 60 mΩ·cm 2 ; thus, at the same thickness, the separator according to the present invention has an ER of about 48 mΩ·cm 2will have an ER value less than. The separator described in the present specification with low ER is owned by Daramic, LLC and can have any or all of the features described in U.S. Provisional Patent Application No. 62 / 319,959, filed on April 8, 2016, which is hereby incorporated by reference in its entirety. The separator described in the present specification with low ER is owned by Daramic, LLC and can have any or all of the features described in U.S. Provisional Patent Application No. 62 / 319,959, filed on April 8, 2016, which is hereby incorporated by reference in its entirety.

[0136] According to at least the selected embodiments, the present disclosure is directed to improved lead-acid batteries such as flooded lead-acid batteries, improved systems comprising lead-acid batteries, and / or battery separators, improved battery separators, improved vehicles comprising such systems, manufacturing or use methods, or combinations thereof. According to at least certain embodiments, the present disclosure is directed to improved flooded lead-acid batteries for such batteries, improved battery separators, and / or manufacturing methods, testing methods, or use methods of such improved flooded lead-acid batteries, or combinations thereof. Additionally, methods, systems, batteries, and / or battery separators for reducing stratification, improving battery life and performance of flooded lead-acid batteries are disclosed herein.

[0137] An exemplary separator as disclosed herein may preferably be characterized by having or providing improved conductivity over time. Conductivity can be determined, for example, as cold cranking amps (CCA) measured with a Midtronics tester. For example, a lead-acid battery comprising the separator of the present invention can show a CCA decrease of less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% over a 30-day period when measured with a Midtronics CCA tester.

[0138] The porous membrane can be provided with additives, surfactants, reagents, fillers, or additives in various ways. For example, when finishing this (e.g., after extraction) and / or adding it to the mixture used in the production of the membrane, the additive(s) may be applied to the porous membrane. According to a preferred embodiment, the additive or additive solution is applied to the porous membrane surface. In particular, this variant is suitable for the application of additives that are not stable to heat and additives that are soluble in the solvents used in subsequent extraction. Particularly suitable as solvents for the additives according to the present invention are methanol and ethanol, as well as mixtures of these alcohols and water and other low molecular weight alcohols. Coating can be performed on the side facing the negative electrode of the microporous membrane, the side facing the positive electrode, or both sides.

[0139] The microporous membrane may be immersed in the additive or additive solution, and then, if necessary, the coating may be performed by removing the solvent, for example, by drying. In this method, the application of the additive can be combined with extraction, which is often applied during separator production.

[0140] Another preferred option is to mix the additive(s) into a mixture of a thermoplastic polymer and, if necessary, a filler and other additives used in the production of the porous membrane. Then, a homogeneous additive-containing mixture is formed into a web-like material.

[0141] The separator of the present invention may be a low-ER separator, a low-water-loss separator, and / or have at least a portion with protrusions, intermittent ribs, serrated ribs, discontinuous ribs, and / or the like (not solid ribs), which can improve acid mixing or the conductivity of the separator. Examples of the protrusions include forms such as short rib regions, nubs, embossments, and the like. The protrusions can be present on either or both surfaces of the separator. Typically, the protrusions will be present on at least the side surface facing the positive electrode plate (positive electrode active material or PAM). The protrusions can be arranged in rows, and the protrusions in each row can be spaced from each other and from the protrusions in adjacent rows. In some cases, the protrusions can be arranged on the side surface of the separator facing the positive electrode active material, the side surface of the separator facing the negative electrode active material (or NAM), or both surfaces of the separator.

[0142] The separator of the present invention can be provided in any form such as in the form of a sheet or a small piece separator, wrap, sleeve, pocket, envelope, hybrid envelope, plate wrap, plate silver wrap (e.g., a fiber mat described herein used as a positive electrode plate, silver wrap, plate wrap, boot, and a system comprising a separator around a plate wrap and / or an adjacent negative electrode plate, e.g., in a 5-point battery system, e.g., a plate silver wrap under a plate wrap). In some embodiments, a microporous membrane that can cover at least one side in at least one fiber layer is provided as a pocket or an envelope. When a fiber layer is present, the microporous membrane preferably has a larger surface area than the fiber layer. Thus, when combining the microporous membrane and the fiber layer, the fiber layer does not completely cover the microporous membrane. At least two opposing end regions of the membrane layer remain uncovered, providing ends for heat sealing to facilitate the formation of a pocket or an envelope. The separator can be processed to form a hybrid envelope. A hybrid envelope can be formed by folding the separator sheet in half and forming one or more slits or openings before, during, or after joining the ends of the separator sheet to form an envelope. The sides are joined using a weld or a mechanical seal to form a seam that brings one side of the separator sheet into contact with the other side of the separator sheet. For example, welding can be performed using heat or ultrasonic treatment. This process results in an envelope shape with a folded end at the bottom and two lateral ends.

[0143] The separator disclosed in the specification in the form of an envelope is a hybrid envelope and may have one or more slits or openings along the folded or sealed creases of the envelope. The length of the opening can be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the length of the entire end portion. The length of the opening can be from 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 ~1 / 5 of the length of the entire end portion. The hybrid envelope can have 1 to 5, 1 to 4, 2 to 4, 2 to 3, or 2 openings, and may or may not be equally arranged along the length of the bottom end portion. It is preferable that there are no openings at the corners of the envelope. The slit may be cut after folding and sealing the separator to obtain an envelope, or the slit may be formed before forming a porous membrane on the envelope.

[0144] The separator as disclosed in the present specification may be characterized by an improved conductance over time. The conductance can be determined, for example, as the cold cranking ampere (CCA) measured with a Midtronics tester. For example, a lead-acid battery equipped with the separator of the present invention, when measured with a Midtronics CCA tester, can show a CCA decrease of less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% over a period of 30 days. In contrast, the CCA decrease observed for a conventional battery under similar conditions is often much larger.

[0145] The separators provided herein enable the manufacture of batteries having reduced water loss and reduced float current of the battery as compared to batteries manufactured from conventional separators. In some embodiments, the water loss can be reduced by more than 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%. In some embodiments, the float current can be reduced by more than 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%. Batteries manufactured using the disclosed separators exhibit a reduction in the increase of internal resistance over time and, in some cases, exhibit no increase in internal resistance.

[0146] In addition to providing reduced water loss and extended battery life, any desirable separator is designed to provide other advantages. With respect to the assembly, the separator has a negative-side cross rib design to maximize bending stiffness and ensure maximum manufacturing productivity. To prevent short circuits during high-speed assembly and in the later stages of life, the separator has excellent resistance to breakage and oxidation compared to standard PE separators.

[0147] According to at least selected embodiments, the present disclosure or invention is directed to improved battery separators, low ER or high conductivity separators, improved lead-acid batteries such as flooded lead-acid batteries, high conductivity batteries, and / or improved vehicles comprising such batteries, and / or methods of manufacturing or using such separators or batteries, and / or combinations thereof. According to at least certain embodiments, the present disclosure or invention is directed to improved lead-acid batteries incorporating improved separators and exhibiting increased conductivity.

[0148] Improved separators described herein, such as the intermittent rib separators described herein, can help prevent the formation of sulfation crystals and provide a more uniform heat distribution and / or heat mixing and / or heat (thermal) across the separator It may also be possible to help provide heat dissipation (dissipating heat in a shorter time compared to known separators such as separators with solid ribs for flooded lead-acid batteries). The exemplary intermittent rib separators described herein may provide improved or faster or more efficient filling of flooded lead-acid batteries, gel batteries, and / or enhanced flooded batteries.

[0149] In various embodiments, the separators disclosed herein are low electrical resistance ("ER") separators. In such embodiments, the separator may include improvements such as an improved filler that increases porosity, pore size, internal pore surface area, wettability and / or the surface area of the separator. In some embodiments, the improved filler has a higher-order structure and / or a reduced particle size and / or a different amount of silanol groups than known fillers and / or more hydroxylation than known fillers. The improved filler may allow for a greater uptake of process oil during separator formation without more oil absorption and / or without shrinking or compressing when removing oil after extrusion. By way of example, the improved separator may be made using silica having an inherent oil absorption of about 175 - 350 ml / 100 g, in some embodiments 200 - 350 ml / 100 g, in some embodiments 250 - 350 ml / 100 g, and in some further embodiments 260 - 320 ml / 100 g, although other oil absorption amounts are also possible.

[0150] ​The separator contains one or more performance-improving additives. The performance-improving additives can be surfactants. Certain suitable surfactants are nonionic, while other suitable surfactants are anionic. The additive can be a single surfactant or a mixture of two or more surfactants, for example, two or more anionic surfactants, two or more nonionic surfactants, or at least one ionic surfactant and at least one nonionic surfactant. By using these specific suitable surfactants together with the separator of the present invention described herein, a further improved separator can be obtained, which, when used in a lead-acid battery, results in reduced water loss, reduced antimony poisoning, improved cycling, reduced float current, reduced float potential, and / or the like with respect to the lead-acid battery. Suitable surfactants include salts of alkyl sulfates; alkylaryl sulfonates; alkylphenol-alkylene oxide addition products; soaps; surfactants such as alkylnaphthalene sulfonates; anionic sulfosuccinates; one or more sulfosuccinates such as dialkyl esters of sulfosuccinates; amino compounds (primary, secondary or tertiary amines; quaternary amines); block copolymers of ethylene oxide and propylene oxide; various polyethylene oxides; and salts of mono- and dialkyl phosphates. Additives include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and their formulations, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone-based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters, and sucrose esters of fatty acids.

[0151] The battery separator can be combined with additives, reagents, and / or fillers in various ways. When this is done (e.g., after extraction and / or rubber introduction) and / or added to the mixture used to finally manufacture the separator by extrusion, the additive(s) can be applied to the separator, for example. According to certain preferred embodiments, the additive or additive solution (such as an aqueous solution) is applied to one or more surfaces of the separator. In particular, this variant is suitable for the application of additives that are not thermally stable and additives that are soluble in the solvents used for the extraction of process oils. 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. The application can be carried out on the side surface facing the negative electrode of the separator, the side surface facing the positive electrode, or both side surfaces. The application can also be carried out during the extraction of the pore former in a solvent bath. In some embodiments, the additive can be combined with the microporous membrane using any of the aforementioned methods, either before or after the introduction of the rubber component. In certain selected embodiments, part of the performance-improving additive such as a surfactant coating or the performance-improving additive (or both) added to the extruder before manufacturing the separator can bind to the antimony in the battery system, inactivate it, and / or form a compound with it, and / or drop it into the mud space of the battery, and / or prevent it from forming a film on the negative electrode.

[0152] In certain embodiments, the additive (non-ionic surfactant, anionic surfactant, or a mixture thereof) is at least 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 / m 2 , 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 If or 10.0 g / m 2 or even about 20.0 g / m 2 It can be present at the following density or impregnation level. The additive is 0.5 - 15 g / m 2 , 0.5 - 10 g / m 2 , 1.0 - 10.0 g / m 2 , 1.5 - 10.0 g / m 2 , 2.0 - 10.0 g / m 2 , 2.5 - 10 .0 g / m 2 , 3.0 - 10.0 g / m 2 , 3.5 - 10.0 g / m 2 , 4.0 - 10.0 g / m 2 , 4.5 - 10.0 g / m 2 , 5.0 - 10.0 g / m 2 , 5.5 - 10.0 g / m 2 , 6.0 - 10.0 g / m 2 , 6.5 - 10.0 g / m 2 , 7.0 - 10.0 g / m 2 , 7.5 - 10.0 g / m 2 , 4.5 - 7.5 g / m 2 , 5.0 - 10.5 g / m 2 , 5.0 ~11.0 g / m 2 , 5.0 - 12.0 g / m 2 , or 5.0 - 15.0 g / m 2 of density or impregnation level. It can be present at

[0153] Immerse the battery separator in an additive or an additive solution (solvent bath addition), and if necessary, perform the coating by removing the solvent, for example, by drying. In this method, the application of the additive can be combined with extraction, which is often applied during film manufacturing, for example. Other preferred methods are spraying the additive onto the surface, dip-coating, roller coating, or curtain coating one or more additives onto the separator surface.

[0154] Another preferred option is to mix the additive(s) in a mixture of a thermoplastic polymer and, if necessary, a filler and other reagents or additives used in the manufacture of the membrane. Then, form the additive-containing mixture into a web-like material.

[0155] In certain embodiments described herein, a reduced amount of an anionic or nonionic surfactant is added to the separator of the present invention. In such cases, the desired characteristics may include a low total organic carbon (TOC) content and / or low volatile organic compounds (VOCs) (due to the lower amount of surfactant), which can produce the desired separator according to such embodiments. In certain embodiments, the additive can be represented by a compound of formula (I).

[0156]

Chemical formula

[0157] Wherein: R is a non-aromatic hydrocarbon radical having 10 to 4200 carbon atoms, preferably 13 to 4200 carbon atoms, which may be interrupted by an oxygen atom;

[0158]

Chemical formula

Chemical formula

[0159] Preferably, it is H, and k = 1 or 2; M is an alkali metal or alkaline earth metal ion, H + or NH4 + and not all variables M simultaneously have the meaning of H + ; n = 0 or 1; m = 0 or an integer from 10 to 1400; and x = 1 or 2.

[0160] 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 simultaneously. However, preferably, only one of the variables n and m is different from 0.

[0161] The non-aromatic hydrocarbon radical means a radical that does not contain an aromatic group and is not aromatic itself. The hydrocarbon radical can be interrupted by oxygen (for example, containing one or more ether groups).

[0162] R is preferably a linear or branched aliphatic hydrocarbon radical that can be interrupted by an oxygen atom. Saturated, non-bridged hydrocarbon radicals are very particularly preferred.

[0163] By using the compound of formula (I) for the production of battery separators, they can be effectively protected against oxidative degradation. R is a hydrocarbon radical having 10 to 180, preferably 12 to 75, very particularly preferably 14 to 40 carbon atoms, and the hydrocarbon radical can be interrupted by 1 to 60, preferably 1 to 20, very particularly preferably 1 to 8 oxygen atoms, and particularly preferably, the formula R 2 -[(OC2H4) p (OC3H6) q - hydrocarbon radical, wherein: R 2 has 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 2 An alkyl radical having 0 carbon atoms; p is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; and q is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; Compounds in which the sum of p and q is from 0 to 10, particularly 0 to 4, are particularly preferred; n = 1; and m = 0, A battery separator containing a compound of formula (I) is preferred.

[0164] The formula R2-[(OC2H4)p(OC3H6) q - is to be understood to include also compounds in which the order of the groups within the brackets is different from that shown. For example, according to the invention, compounds in which the radicals within the brackets are formed by alternating (OC2H4) groups and (OC3H6) groups are suitable. Compounds in which the radicals within the brackets are formed by alternating (OC2H4) groups and (OC3H6) groups are suitable. For example, according to the invention, compounds in which the radicals within the brackets are formed by alternating (OC2H4) groups and (OC3H6) groups are suitable.

[0165] Additives in which R2 is a straight-chain or branched-chain alkyl radical having 10 to 20, preferably 14 to 18 carbon atoms, have been found to be particularly advantageous. OC2H4 is preferably OCH2CH2, and OC3H6 is OCH(CH3)2 and / or OCH2CH2CH3.

[0166] Preferred additives include, in particular, alcohols (p = q = 0; m = 0), Primary alcohols are particularly preferred, and fatty alcohol ethoxylates (p = 1 to 4, q = 0), fatty alcohol propoxylates (p = 0; q = 1 to 4) and fatty alcohol alkoxylates (p = 1 to 2; q = 1 to 4) ethoxylates of primary alcohols are preferred. Fatty alcohol alkoxylates are obtained, for example, by reaction of the corresponding alcohol with ethylene oxide or propylene oxide.

[0167] Additives of the type with m = 0 which are insoluble or only sparingly soluble in water and sulfuric acid have been found to be particularly advantageous. R is an alkane radical having 20 to 4200, preferably 50 to 750, very particularly preferably 80 to 225 carbon atoms. M is an alkali metal or alkaline earth metal ion, H + or NH4 + and in particular L i + , Na + and K + or H + such as alkali metal ions, and not all variables M simultaneously have the meaning of H + ; n = 0; m is an integer from 10 to 1400; and x = 1 or 2, Additives containing compounds of formula (I) are also preferred.

[0168] Suitable additives include, in particular, polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers, and these acid groups are at least partially (e.g., preferably 40%, particularly preferably 80%) neutralized. The percentage represents the number of acid groups. Highly preferred is poly(meth)acrylic acid present in completely salt form. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium (NR4 where R is either hydrogen or a carbon functional group). Poly(meth)acrylic acid means polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acid is preferred, in particular polyacrylic acid having an average molar mass Mw of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, very particularly preferably 1,000 to 4,000 g / mol. The molecular weight of poly(meth)acrylic acid polymers and copolymers is confirmed by measuring the viscosity of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution (Fikentscher constant).

[0169] (Meth)acrylic acid copolymers, especially those containing, in addition to (meth)acrylic acid, ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and / or 2-ethylhexyl acrylate as comonomers, are also suitable. Copolymers containing at least 40% by weight, preferably at least 80% by weight, of (meth)acrylic acid monomer are preferred, and the percentage is based on the acid form of the monomer or polymer.

[0170] For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, especially sodium hydroxide, are particularly suitable. In addition, coatings and / or additives for strengthening the separator may be, for example, by way of example only (not limiting), metal alkoxides such as Zn, Na, or Al may be, and sodium ethoxide can be cited as an example.

[0171] In some embodiments, the microporous polyolefin separator layer may comprise a coating on one or both sides of such a layer. Such coatings may include surfactants or other materials. In certain embodiments, the coating is combined with the membrane before or after rubber addition, or both before and after rubber addition. In some embodiments, the coating may comprise, for example, one or more materials described in U.S. Patent No. 9,876,209 (B2), incorporated herein by reference. Such coatings may, for example, reduce the overcharge voltage of the battery system, thereby reducing grid corrosion, preventing dry-out and / or water loss, and extending battery life.

[0172] The improved separator is useful for various batteries, particularly for lead-acid batteries. The battery can be a flooded battery and can be a tubular or flat plate battery. The battery can be used in transportation applications such as golf cart (sometimes called golf car) batteries, or in other deep cycle applications such as solar or wind batteries.

[0173] A battery comprising the improved separator disclosed herein, particularly a flooded lead-acid battery, particularly a deep cycle battery, can be characterized by a lower float current (amperes) after charging a 12-volt battery (or 2.4 volts per cell, a 12-volt battery having six cells) at a float voltage of 14.4 volts for a given time such as 21 days, and the test can be extended up to 84 days measured at 21-day intervals.

[0174] In addition, the battery separator of the present invention disclosed and described herein provides an improved deep cycle battery that uses these at a more constant and lower end-of-charge (EOC) current. Maintaining a lower EOC current has been shown to indicate Sb poisoning suppression in the improved batteries described herein. By way of example, as the life of a new deep cycle lead-acid battery, more Sb may be present in the battery and the EOC current can increase over the life of the battery, which in turn decreases the overall life cycle performance of the battery by increasing the water consumption of the battery. The separator of the present invention described herein means that the EOC current is maintained more consistently over the entire cycle life of the battery.

[0175] The end-of-charge current is sometimes referred to as the float current necessary to maintain the fixed voltage of a lead-acid battery during the idle period. In lead-acid batteries containing antimony, they exhibit typical behavior with conventional lead-acid battery separators; antimony poisoning is observed by measuring the increase in the end-of-charge current over the life cycle. Antimony-suppressing battery separators currently on the market or of the current state-of-the-art reduce antimony poisoning to some extent. However, the separator discovered according to the present invention can satisfy or even suppress the current state-of-the-art. The separators disclosed herein provide at least antimony suppression levels equivalent to, but often better than, the current state-of-the-art while further reducing the end-of-charge current below that of the current state-of-the-art.

[0176] Briefly, when used in a flooded lead-acid battery such as a deep-cycle flooded lead-acid battery, the improved flexible battery separator described and claimed herein, which includes at least one performance enhancing additive and / or coating, provides improved and even significantly improved deep-cycle flooded lead-acid batteries with respect to antimony suppression compared to batteries manufactured using separators made entirely of rubber and compared to batteries manufactured using separators that do not contain rubber and / or latex components (measured by the end-of-charge (EOC) voltage and indicated by improved EOC voltage suppression). With respect to antimony suppression, antimony poisoning can occur from the onset of operation of a lead-acid battery such as a flooded lead-acid battery such as a deep-cycle flooded lead-acid battery. However, over the life of the battery, more antimony is released from the repeated operation of the battery, meaning that antimony suppression becomes even more critical later in the battery life. The improved separators described herein address the same issues of acting to suppress antimony towards the end of the battery life, for example, beyond 50% of the intrinsic or intended battery life. which act to suppress antimony.

[0177] In addition, the improved soft battery separator described herein exhibits a reduction in float charge current at steady state potential compared to batteries manufactured using previously known separators; a reduction in voltage and / or energy required to recharge a deep cycle operation battery to full charge compared to deep cycle batteries manufactured using previously known separators; improved overall voltage control compared to batteries manufactured using previously known separators; and / or a reduction in grid corrosion compared to batteries manufactured using previously known separators, and also provides a deep cycle flooded lead acid battery.

[0178] In addition, in experiments using the separator of the present invention, it has been found that the Sb poisoning effect is reduced for batteries using the separator of the present invention. The Sb poisoning effect manifests itself as a decrease in the hydrogen evolution overpotential or an increase in the hydrogen evolution rate by electrochemically reduced water. This overpotential can be measured by measuring the hydrogen evolution current at a fixed potential, and such experiments have shown that the separator according to the present invention exhibits better performance than known separators. Similar experiments have also found that there is a difference in the large anode (positive current) peak associated with the CV curve for batteries equipped with the separator according to the present invention. Such a peak is due to the oxidation of Pb to PbSO4 on the surface of the lead working electrode. Regarding the conventional comparative separator it was found that peak one was shifted 40 - 60 mV to the plus side, which may be due to the presence of Sb on the surface where the chemical change from Pb to PbSO4 occurs. For the battery equipped with the separator according to the present invention a smaller shift in the peak position was observed, which indicates suppression of Sb on the lead surface. This observation of an apparent decrease in the hydrogen evolution rate indicates that the separator according to the present invention is a reduction in the film formation of Sb on the negative (lead) electrode.

[0179] An improved separator for lead acid batteries is disclosed herein. The separator may include a porous membrane, rubber and / or latex, and at least one performance enhancing additive or surfactant.

[0180] According to at least selected embodiments, aspects or objectives, the present disclosure or the present invention discloses or provides herein a novel or improved separator, battery separator, reinforced liquid battery separator, battery, cell, and / or a method of manufacturing and / or using such separator, battery separator, reinforced liquid battery separator, cell and / or battery. According to at least certain embodiments, the present disclosure or the present invention is directed to a novel or improved battery separator for a reinforced liquid battery. In addition, methods, systems and battery separators for enhancing battery life, reducing internal electrical resistance, increasing cold cranking amps, and / or improving at least the uniformity within a reinforced liquid battery are disclosed herein. According to at least certain embodiments, the present disclosure or the present invention is directed to an improved separator for a reinforced liquid battery, wherein the separator has a performance enhancing additive or coating, an improved filler, reduced twist, improved wettability, reduced oil content, reduced thickness, reduced electrical resistance, and / or increased porosity, and the use of such separator in a battery reduces water loss of the battery, lower stratification of the battery, lower voltage drop of the battery, and / or reduces the CCA of the battery. According to at least certain embodiments, a separator is provided that includes or exhibits a performance enhancing additive or coating, increased porosity, increased pore volume, amorphous silica, high oil absorption silica, high silanol group silica, antimony poisoning resistance, electrolyte mixing, active material retention on the electrode, and any combination thereof.

[0181] According to at least certain embodiments, the present disclosure or the present invention is directed to an improved flooded lead acid battery for such a battery, an improved battery separator, mat, composite separator, laminated separator, positive envelope, negative envelope, and / or the like, and / or a method of manufacturing, testing or using such an improved flooded lead acid battery, or a combination thereof.

[0182] According to at least certain embodiments, aspects, and / or purposes, the present invention, application, or disclosure can provide solutions, new products, improved products, new methods, and / or improved methods, and / or address the heart, need, and / or problem of PAM shedding, NAM shedding, electrode distortion, active material shedding, active material loss, and / or physical separation, electrode efficiency, battery performance, battery life, and / or cycle life problems, and / or address the challenges arising from current lead-acid batteries or battery systems, and provide a new battery separator, new battery technology, and / or new battery method and / or system, preferably or particularly a reinforced flooded lead-acid battery, PSoC battery, ISS battery, ESS battery, and / or the like, particularly a reinforced flooded lead-acid battery, or other flooded batteries, AGM batteries, PSoC batteries, ISS batteries, ESS batteries, or the like, a new battery separator, new battery technology, and / or new battery method and / or system that can prevent or delay the shedding of active material from the electrodes of other batteries.

[0183] In at least one possible preferred embodiment, the separator comprises a fiber mat for retaining the active material on the electrodes of the lead-acid battery. In at least one particularly preferred possible embodiment, the PE film separator comprises at least one fiber mat for retaining the active material on the electrodes of the lead-acid battery. Also disclosed, shown, claimed, and / or provided are novel or improved mats, separators, batteries, methods, and / or systems. For example, according to at least certain embodiments, aspects, and / or purposes, the present invention, this application, or this disclosure can provide solutions, novel products, improved products, novel methods, and / or improved methods, and / or address the heart, need, and / or problems of PAM shedding, NAM shedding, electrode distortion, active material shedding, active material loss, and / or physical separation, electrode efficiency, battery performance, battery life, and / or cycle life problems, and / or address the challenges arising from current lead-acid batteries or battery systems with novel battery separators, novel battery technologies, and / or novel battery methods and / or systems, preferably or particularly in enhanced flooded lead-acid batteries, PSoC batteries, ISS batteries, ESS batteries, or the like, and in particular novel battery separators, novel battery technologies, and / or novel battery methods and / or systems that can prevent or delay the shedding of active material from the electrodes.

[0184] In at least one embodiment, the separator comprises a fiber mat for retaining the active material on the electrodes of a lead-acid battery. Also disclosed, shown, claimed, and / or provided are novel or improved mats, separators, batteries, methods, and / or systems. For example, in at least one possible preferred embodiment, the composite separator comprises a fiber mat for retaining the active material on the electrodes of a lead-acid battery. In at least one possible particularly preferred embodiment, the PE membrane separator comprises at least one fiber mat for retaining the active material on the electrodes of a lead-acid battery. According to at least certain embodiments, aspects, and / or purposes, the present invention, application, or disclosure can provide solutions, novel products, improved products, novel methods, and / or improved methods, and / or address the core, requirements, and / or problems of PAM shedding, NAM shedding, electrode distortion, active material shedding, active material loss, and / or physical separation, electrode efficiency, battery performance, battery life, and / or cycle life problems and / or can address the challenges arising from current lead-acid batteries or battery systems, and / or can provide novel battery separators, novel battery technologies, and / or novel battery methods and / or systems, preferably or particularly in flooded lead-acid batteries, enhanced flooded lead-acid batteries, PSoC batteries, ISS batteries, ESS batteries, and / or the like, particularly novel battery separators, novel battery technologies, and / or novel battery methods and / or systems that can prevent or retard the shedding of active material from the electrodes.

[0185] According to at least a selected embodiment, aspect, or objective, the present disclosure or invention can be directed to, or provide, a novel or improved separator, battery separator, reinforced liquid battery separator, fiber mat, battery, cell, and / or a method of manufacturing and / or using such separator, battery separator, fiber mat, reinforced liquid battery separator, cell, and / or battery. According to at least certain embodiments, the present disclosure or invention can be directed to a novel or improved reinforced liquid lead-acid battery separator, fiber mat, liquid battery for deep cycle applications, and / or reinforced liquid battery, and / or system, vehicle, and / or the like, including such separator, mat, or battery, and / or an improved method of manufacturing and / or using such improved separator, mat, cell, battery, system, vehicle, and / or the like. According to at least certain embodiments, the present disclosure or invention can be directed to an improved separator for a reinforced liquid battery and / or an improved method of manufacturing and / or using such battery comprising such improved separator. According to at least a selected embodiment, the present disclosure or invention can be directed to a separator, particularly a separator for a reinforced liquid battery having low electrical resistance and / or high cold cranking amps. Additionally, methods, systems, and battery separators for enhancing battery life, reducing water loss, reducing internal resistance, improving wettability, reducing stratification, improving acid diffusion, improving cold cranking amps, and / or at least improving uniformity within a reinforced liquid battery are disclosed herein. According to at least certain embodiments, the present disclosure or invention can be directed to an improved separator for a reinforced liquid battery, the separator comprising one or more performance enhancing additives or coatings, increased porosity, increased pore volume, amorphous silica, high oil absorption silica, high silanol group silica, retention and / or improved retention of active material on an electrode, and / or any combination thereof.

[0186] The compositions and methods of the appended claims are not limited to the specific compositions and methods described herein, are intended as illustrations of only a few aspects of the claims, and any compositions and methods that are functionally equivalent are within the scope of the claims. Various changes to the compositions and methods in addition to those shown and described herein are within the scope of the appended claims. Further, while only specific representative compositions and method steps disclosed herein are explicitly described, other combinations of compositions and method steps, even if not specifically recited, are within the scope of the appended claims. Accordingly, steps, elements, or combinations of elements may or may not be explicitly recited herein, but other combinations of steps, elements, and components are included even if not explicitly specified.

[0187] The present invention may be embodied in other forms without departing from its gist and essential attributes, and thus reference should be made to the appended claims, which indicate the scope of the invention rather than the foregoing description. What is disclosed are the components that may be used to perform the disclosed methods and systems. These and other components are disclosed herein, and when combinations, subsets, interactions, groups, etc. of these are disclosed, specific references to each various individual and collective combination and permutations thereof need not be explicitly disclosed, and each is specifically contemplated and understood to be described herein with respect to all methods and systems. This applies to all aspects of the present application including, but not limited to, steps in the disclosed methods. Thus, if there are various additional steps that can be performed, it is understood that each of these additional steps may be performed in any particular embodiment or combination of embodiments of the disclosed methods.

[0188] ​The foregoing description of the structure and method is shown for illustrative purposes only. The exemplary embodiments, including the best mode, are disclosed using examples, and enable any person skilled in the art to practice the invention, including the manufacture and use of any device or system and the implementation of any incorporated method. These examples neither cover nor limit the invention in practicing the disclosed steps and / or forms, 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 methods described herein may be performed in any order that is physically possible. The patent scope of the present invention is defined by the appended claims and may include other embodiments that will occur to those skilled in the art. Such other embodiments shall be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that differ from the literal language of the claims only by insubstantial amounts.

[0189] The compositions and methods of the appended claims are not limited to the scope by the specific compositions and methods described herein, but are intended to be illustrative of a few aspects of the claims. Any compositions and methods that are functionally equivalent shall be within the scope of the claims. Various modifications to the compositions and methods in addition to those shown and described herein shall be within the scope of the appended claims. Further, although only specific representative compositions and method steps disclosed herein are explicitly described, other combinations of compositions and method steps, even if not specifically described, shall be within the scope of the appended claims. Therefore, combinations of steps, components, or ingredients may or may not be explicitly stated herein, but other combinations of steps, components, and ingredients are included even if not explicitly specified.

[0190] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include the plural unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from one particular value and / or to the other particular value. Similarly, when values are approximated by use of the antecedent "about", the particular value is understood to form another embodiment. It will be further understood that each of the endpoints of a range is significant both in relation to the other endpoint and independently of the other endpoint. "Optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and that the specification includes instances where the event or circumstance occurs and instances where it does not.

[0191] Throughout this specification and the claims thereof, variations of the terms "comprise", "comprising", "comprises", and the like are to be construed as meaning "including but not limited to", e.g., not excluding other additives, components, integers, or steps, etc. The terms "consisting essentially of" and "consist The term “consisting of” may be used in place of “comprising” and “including” to provide more specific embodiments of the present invention and is also disclosed. “Exemplary” or “for example” means “an example of” and does not convey a preference for or an indication of an ideal embodiment. Similarly, “such as” is not used in its respective sense but is used for illustrative or exemplary purposes. Except as otherwise noted or in the case of examples, all numbers, reaction conditions, etc. representing component amounts used in this specification and the claims should be understood as being, at a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the claims, and should be interpreted in light of the number of significant digits and ordinary rounding approaches.

[0192] Except as otherwise noted, all numbers representing geometries, dimensions, etc. used in this specification and the claims should be understood as being, at a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the claims, and should be interpreted in light of the number of significant digits and ordinary rounding approaches.

[0193] Unless otherwise specified, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention pertains. The documents cited herein and the materials to which they refer are incorporated by reference in particular.

[0194] In addition, the present invention, as appropriately disclosed herein by way of illustration, may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. 1. A lead acid battery separator assembly, comprising: A separator layer; A nonwoven fiber mat; With the fiber mat is disposed adjacent to the separator layer; and The fiber mat has a resistivity of about 6 mΩ·cm 2 ~Approx. 14mΩ・cm 2 an average pore size of less than about 5 and an electrical resistivity of about 1500 l / m 2 s ~ approx. 2500l / m 2 s range of air permeability, Lead acid battery separator assembly.

2. 10. The lead acid battery separator assembly of claim 1, wherein the separator layer and the fiber mat are laminated together.

3. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a thickness of about 200 μm to 450 μm.

4. The fiber mat has a resistivity of about 11 mΩ·cm 2 2. The lead of claim 1 having an electrical resistance of less than Battery separator assembly.

5. The fiber mat has a thickness of about 50 g / m 2 ~Approx. 65g / m 2 10. The lead acid battery separator assembly of claim 1 having an areal weight in the range of

6. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a preferred binder percentage ranging from about 15% to about 21% by weight.

7. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a longitudinal tensile strength of about 200 N / 50 mm.

8. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a cross tensile strength of about 150N / 50mm.

9. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat comprises a synthetic fiber diameter of about 7.2 μm.

10. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat comprises fibers selected from the group consisting of glass fibers, synthetic fibers, and combinations thereof.

11. 11. The lead acid battery separator assembly of claim 10, wherein said synthetic fibers are selected from the group consisting of polypropylene, polyethylene terephthalate, acrylic, other plastics, polymers, homopolymers, copolymers, and any combination thereof.

12. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat comprises an additive selected from the group consisting of rubber, silica, soluble fiber, gelling agents, surfactants, and combinations thereof.

13. 13. The lead acid battery separator assembly of claim 12, wherein the additive is selected from the group consisting of applied as a coating, impregnated into the fiber mat, dispersed within the fiber mat, added during manufacture of the porous membrane, and any combination thereof. 。

14. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer and said fiber mat are leaves.

15. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer and said fiber mat are a sleeve.

16. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer and said fiber mat are an envelope.

17. 17. The lead acid battery separator assembly of claim 16, wherein said envelope is a hybrid envelope.

18. the separator layer is a microporous membrane; the separator layer comprises polyethylene, preferably ultra-high molecular weight polyethylene, a particulate filler, and a processing plasticizer; the separator layer comprises a particulate filler in an amount of 40% by weight or more of the separator layer; and The polyethylene comprises a polymer having a shish-kebab structure formation, which comprises a plurality of extended chain crystals (shish structure formation) and a plurality of folded chain crystals (kebab structure formation), and the average repeat or periodicity of the kebab structure formation is between 1 nm and 150 nm; 10. The lead acid battery separator assembly of claim 1.

19. the filler is selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica, and any combination thereof; 29 20. The lead acid battery separator assembly according to claim 18, wherein the molar ratio of OH to Si groups in said filler is within the range of about 21:100 to 27:100 or more as measured by Si-NMR.

20. 20. The lead acid battery separator assembly of claim 18, wherein said microporous membrane has a porosity greater than about 64%.

21. 20. The lead acid battery separator assembly of claim 18, wherein said processing plasticizer is selected from the group consisting of processing oil, paraffinic mineral oil, mineral oil, and any combination thereof.

22. 20. The lead acid battery separator assembly of claim 18, wherein said particulate filler is present in a kebab structure formation of said polymer.

23. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer is selected from the group consisting of polyolefins, polyethylene, polypropylene, rubber, polyvinyl chloride, phenolic resins, cellulosic materials, synthetic wood pulp, fiberglass, synthetic fibers, and combinations thereof.

24. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer comprises one of the group consisting of a filler, a surfactant, and combinations thereof.

25. 14. The lead acid battery separator assembly according to claim 13, wherein said surfactant is selected from the group consisting of non-ionic surfactants, ionic surfactants, and anionic surfactants.

26. 2. The lead acid battery separator assembly of claim 1, wherein said separator layer includes one of the group consisting of ribs, interrupted ribs, serrated ribs, embattled ribs, embossed ribs, negative cross ribs, and any combination thereof.

27. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer includes a plurality of interrupted ribs, said plurality of interrupted ribs being defined by an angular orientation.

28. 28. The lead acid battery separator assembly of claim 27, wherein said angular orientation is with respect to a machine direction of said separator layer, and said angular orientation is at an angle selected from the group consisting of greater than zero degrees (0°) and less than one hundred and eighty degrees (180°), and greater than one hundred and eighty degrees (180°) and less than three hundred and sixty degrees (360°).

29. 26. The lead acid battery separator assembly of claim 25, wherein said separator layer includes one or more sets of ribs within said plurality of interrupted ribs; a first set of ribs within said one or more sets of ribs having a first angular orientation; and a second set of ribs within said one or more sets of ribs having a second angular orientation.

30. 10. The lead acid battery separator assembly of claim 1, wherein said separator layer comprises rubber.

31. 31. The lead acid battery separator assembly of claim 30, wherein said rubber is selected from the group consisting of latex, methyl rubber, polybutadiene, chloropene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, norbornene rubber, acrylate rubber, fluororubber, silicone rubber, copolymer rubber, and combinations thereof.

32. 32. The lead acid battery separator assembly of claim 31, wherein said copolymer rubber is selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber (EPM and EPDM), ethylene-vinyl acetate rubber, and combinations thereof.

33. 31. The lead acid battery separator assembly of claim 30, wherein said rubber is crosslinked or non-crosslinked.

34. 31. The lead acid battery separator assembly of claim 30, wherein said rubber is coated on at least one side of said separator layer.

35. 31. The lead acid battery separator assembly of claim 30, wherein said rubber is impregnated into said separator layer.

36. 31. The lead acid battery separator assembly of claim 30, wherein said rubber is compounded with a polymer used to form said separator layer.

37. A lead acid battery comprising the lead acid battery separator assembly of claim 1.

38. 38. The lead acid battery of claim 37, wherein the battery comprises a series of alternating positive and negative electrodes; and the positive electrodes comprise an active material.

39. 39. The lead acid battery of claim 38, wherein the separator layer and the fiber mat are interposed between the positive and negative electrodes.

40. 39. The lead acid battery of claim 38, wherein the separator layer and the fiber mat are an envelope surrounding the positive electrode.

41. 41. The lead acid battery of claim 40, wherein the envelope is a hybrid envelope.

42. 40. The lead acid battery of claim 39, wherein the separator layer and the fiber mat are laminated as a single unit.

43. 40. The lead acid battery of claim 39, wherein the separator layer and the fiber mat are adjacent to one another.

44. 40. The lead acid battery of claim 39, wherein the fiber mat is disposed between the separator layer and the positive electrode.

45. 40. The lead acid battery of claim 39, wherein the fiber mat is pressed against the active material.

46. 40. The lead acid battery of claim 39, wherein the fiber mat is embedded in the active material.

47. 40. The lead acid battery of claim 39, wherein the fiber mat is embedded in a paste paper.

48. 38. The lead acid battery of claim 37, wherein the fiber mat has an average pore size smaller than an average particle size of the active material.

49. 38. The lead acid battery of claim 37, wherein the battery is selected from the group consisting of tubular batteries, flat plate batteries, golf cart batteries, inverter batteries, SLI batteries, flooded lead acid batteries, deep cycle batteries, and batteries operated in a partial state of charge.

50. A vehicle comprising the lead acid battery of claim 37.

51. 51. The vehicle of claim 50, wherein the vehicle is selected from the group consisting of a car, a truck, a forklift, a golf cart, an e-rickshaw, and a hybrid electric vehicle (HEV).

52. 51. The vehicle of claim 50, wherein the vehicle is subject to motions characterized by stop and start movements.

53. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a thickness of about 0.3 mm.

54. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a thickness of about 0.2 mm.

55. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a thickness of about 0.4 mm.

56. 10. The lead acid battery separator assembly of claim 1, wherein said fiber mat has a thickness of about 0.1 to about 0.5 mm.

57. 1. A lead acid battery separator, comprising: A porous membrane; A nonwoven fiber mat; With the fibrous mat is disposed adjacent to the porous membrane; and The fiber mat has a thickness of about 6 mΩ cm. 2 ~Approx. 14mΩ・cm 2 Electrical resistance in the range of an average pore size of less than about 5 μm; and Approximately 1500l / m 2 s ~ approx. 2500l / m 2 s range of air permeability, Lead acid battery separator.

58. 1. A lead acid battery separator assembly, comprising: A separator layer; A nonwoven fiber mat; With the fiber mat is disposed adjacent to the separator layer; The fiber mat has a resistivity of about 6 mΩ·cm 2 ~Approx. 14mΩ・cm 2 and an average pore size of less than about 5 μm; said separator layer comprises rubber. Lead acid battery separator assembly.

59. 59. The lead acid battery separator assembly of claim 58, wherein said rubber is selected from the group consisting of latex, methyl rubber, polybutadiene, chloropene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, norbornene rubber, acrylate rubber, fluororubber, silicone rubber, copolymer rubber, and combinations thereof.

60. 60. The lead acid battery separator assembly of claim 59, wherein said copolymer rubber is selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber (EPM and EPDM), ethylene-vinyl acetate rubber, and combinations thereof.

61. 60. The lead acid battery separator assembly of claim 58, wherein said rubber is crosslinked or non-crosslinked.

62. 60. The lead acid battery separator assembly of claim 58, wherein said rubber is coated on at least one side of said separator layer.

63. 60. The lead acid battery separator assembly of claim 58, wherein said rubber is impregnated into said separator layer.

64. 60. The lead acid battery separator assembly of claim 58, wherein said rubber is compounded with a polymer used to form said separator layer.

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