Battery separator and fiber pad assembly, lead-acid battery and vehicle

Abstract

An assembly of a lead acid battery separator and a fibrous mat for a PSoC battery for ISS vehicles wherein an overcharge-sensitive, electrolyte-absorbing fibrous mat is changed from part of an electrode assembly into one unit with the separator; the fiber mat comprises bundled fibers, and the diameter of synthetic fibers of the fiber mat is 7.2 + / -0.5 micrometers and is smaller than the average fiber diameter in the prior art. The average pore size of the fiber pad is smaller than the average particle size of the active material; the fibrous mat has soluble fibers, a wetting agent, and / or a gelling agent. According to the invention, the original function of preventing the active material from falling off from the electrode is maintained, and the function of preventing the electrode from deforming is added. According to the invention, a possible gap between the fiber pad and the battery separator in the prior art is eliminated, the acid stratification of the battery separator is reduced, the wettability of the battery separator is ensured, and the battery separator is prevented from being completely dried at high temperature, so that the battery performance is stabilized, and the service life of the battery is prolonged.

Description

[0001] This application is a divisional application. The priority date of the original PCT application is February 10, 2017; the original international application date is February 9, 2018; the original international application number is PCT / US2018 / 017534; the date of entering the Chinese national phase is September 29, 2019, and the Chinese application number is 201880022914.4; the original invention name is "Improved fiber mat-containing separator, lead-acid battery using the same, and methods and systems related thereto".

[0002] Related Applications

[0003] This application claims priority to and the benefit of co-pending, commonly-owned International Application No. PCT / US2017 / 017418, filed on February 10, 2017. Technical Field

[0004] According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators, battery separators, flooded battery separators, enhanced flooded battery separators, fiber mats, batteries, galvanic cells, and / or methods of making and / or using such separators, battery separators, fiber mats, enhanced flooded battery separators, galvanic cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead acid battery separators, fiber mats, flooded batteries for deep cycle applications, and / or enhanced flooded batteries, and / or systems, vehicles, and / or the like including such separators, mats, or batteries, and / or improved methods of making and / or using such improved separators, mats, galvanic cells, batteries, systems, vehicles, and / or the like. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries and / or improved methods of making and / or using such batteries having such improved separators. According to at least selected embodiments, the present disclosure or invention is directed to separators, flooded battery separators, and in particular separators for enhanced flooded batteries having reduced resistance and / or increased cold cranking current. In addition, methods, systems, and battery separators for improving battery life, reducing water loss, reducing internal resistance, increasing wettability, reducing acid stratification, improving acid diffusion, improving cold cranking current, and / or improving uniformity in at least enhanced flooded batteries are disclosed herein. According to at least particular embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries, wherein the separator comprises one or more performance enhancing additives or coatings, increased porosity, increased void volume, amorphous silica, more oil absorbing silica, more silanol-rich silica, retention and / or improved retention of active materials on electrodes, and / or any combination thereof.

[0005] According to at least selected embodiments, the present disclosure or invention is directed to separators for lead-acid batteries, particularly flooded lead-acid batteries, and various lead-acid batteries, such as flooded lead-acid batteries or enhanced flooded lead-acid batteries, that contain such separators. According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators, galvanic cells, batteries, and / or methods of making and / or using such separators, galvanic 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 having such improved separators. In addition, disclosed herein are methods, systems, and battery separators for increasing battery life, reducing battery failure, reducing water loss, improving oxidation stability, improving, maintaining, and / or reducing float current, improving end of charge (EOC) current, reducing current and / or voltage required to charge and / or fully charge a deep cycle battery, minimizing the increase in internal resistance, reducing resistance, increasing wettability, reducing electrolyte soaking time, reducing battery formation time, reducing antimony poisoning, reducing acid stratification, improving acid diffusion, and / or improving uniformity in a lead-acid battery. According to at least particular embodiments, the present disclosure or invention is directed to an improved separator for a lead-acid battery, wherein the separator includes one or more improved performance enhancing additives and / or coatings. According to at least particular embodiments, the disclosed separators can be used in deep cycle applications, such as in mobile machinery or vehicles and / or stationary machinery or vehicles, such as golf carts, forklifts, inverters, renewable energy systems, and / or alternative energy systems (by way of example only, solar energy systems and wind energy systems). In particular, the disclosed separators are useful in battery systems where deep cycling and / or partial state of charge operation are part of the battery life, and even more particularly, in battery systems where additives and / or alloys (antimony being a key example) are added to the battery to improve the battery's life and / or performance and / or enhance the battery's deep cycling and / or partial state of charge operation capabilities.

[0006] According to at least selected embodiments, the present disclosure is directed to improved lead-acid batteries (e.g., flooded lead-acid batteries), improved systems and / or battery separators comprising lead-acid batteries, improved battery separators, improved vehicles comprising such systems, methods of manufacture or use, or combinations thereof. According to at least certain embodiments, the present disclosure or invention is directed to improved flooded lead-acid batteries, improved battery separators, liners, composite separators, laminated separators, positive electrode packaging, negative electrode packaging, and / or the like for such batteries, and / or methods of manufacture, testing, or use of such improved flooded lead-acid batteries, or combinations thereof. In addition, methods, systems, batteries, and / or battery separators for reducing acid stratification, improving battery life and performance in flooded lead-acid batteries and in such batteries operating at partial states of charge are disclosed herein. Background Art

[0007] To meet the growing demand for power in idle start / stop applications, enhanced flooded batteries (“EFBs”) and absorbed glass mat (“AGM”) batteries have been developed. EFB systems have a similar structure to conventional flooded lead-acid batteries, where the positive and / or negative electrodes are surrounded by a microporous separator and immersed in a liquid electrolyte. AGM systems, on the other hand, do not contain free liquid electrolyte. Instead, the electrolyte is absorbed into a fiberglass mat, which is then laminated on top of the electrodes. Historically, AGM systems have had higher discharge power, better cycle life, and greater cold cranking current than flooded battery systems. However, AGM batteries are significantly more expensive to manufacture and are more sensitive to overcharging. Therefore, EFB systems remain an attractive option for mobile and stationary power for a variety of markets and applications.

[0008] An EFB system may include one or more battery separators, which separate or "partition" the positive electrode from the negative electrode within a lead-acid battery cell. A battery separator may have two main functions. First, the battery separator should keep the positive electrode physically separated from the negative electrode to prevent any electrical current from passing between the two electrodes. Second, the battery separator should allow ion flow between the positive and negative electrodes with as little resistance as possible. Battery separators can be made from a variety of different materials, but these two opposing functions have been well met by battery separators made from porous non-conductors. With this structure, the pores facilitate ion diffusion between the electrodes, and the non-conductive polymer network prevents electrical shorts.

[0009] EFBs with increased discharge power and cold cranking amperes or current ("CCA") will be able to replace AGM batteries. It is known that cold cranking current is associated with the internal resistance of the battery. It is therefore expected that reducing the internal resistance of an enhanced flooded battery will increase the cold cranking current rating. Therefore, new battery separator and / or battery technologies are needed to meet and overcome the challenges posed by current lead-acid battery systems, especially reducing internal resistance and increasing cold cranking current in enhanced flooded batteries.

[0010] To reduce fuel consumption and the generation of tailpipe emissions, automobile manufacturers have implemented varying degrees of electric hybridization. One form of hybrid electric vehicle (HEV) is sometimes referred to as a "micro-HEV" or "micro-hybrid." In such a micro-HEV or similar vehicle, the vehicle may have an idle start / stop (ISS) function, in which the engine can be shut down at various points during idle start / stop and / or regenerative braking. While this increases the fuel economy of the vehicle, it also increases the stress on the battery, which must power additional devices (e.g., air conditioning, media player, etc.) when the vehicle is not in motion.

[0011] Conventional vehicles (e.g., cars without a start / stop feature) may use a conventional flooded lead-acid battery, such as a Start Lighting Ignition (SLI) lead-acid battery. Since the engine is never shut off during use, power is drawn from the battery only when the engine is started. As a result, the battery is often in an overcharged state, rather than a partial state of charge. For example, such a conventional flooded lead-acid battery may exist at a state of charge greater than 95%, greater than 96%, greater than 97%, greater than 98%, greater than 99%, or even greater than 100%, because it is often in an overcharged state. When overcharged, gas bubbles (e.g., hydrogen bubbles) are generated within a conventional lead-acid battery, and these circulating bubbles have the effect of mixing the liquid electrolyte (acid) within the battery.

[0012] On the other hand, a start / stop vehicle is constantly drawing power from the battery, which is therefore always in a partially charged state. When partially charged, bubbles are not generated, so internal mixing of the electrolyte is significantly reduced, leading to acid stratification within the battery. Therefore, acid stratification is a problem in start / stop flooded lead-acid batteries and various enhanced flooded batteries, while acid stratification is not a problem for more conventional or traditional flooded lead-acid batteries that are operated in an overcharged or fully charged (or nearly fully charged) state.

[0013] Acid stratification is a term for the process whereby a higher concentration of sulfuric acid accumulates at the bottom of the cell, resulting in a correspondingly higher water concentration at the top of the cell. In flooded lead-acid batteries, such as enhanced flooded lead-acid batteries or start / stop flooded lead-acid batteries, acid stratification is undesirable. The reduction in acid content at the top of the electrode may inhibit uniformity and charge acceptance within the battery system and may increase the variation in internal resistance from top to bottom along the height of the cell. The increase in acid content at the bottom of the cell artificially increases the cell voltage, which can interfere with the battery management system and may send unintended / false health status signals to the battery management system. In general, acid stratification results in higher resistance of battery components, which may lead to electrode issues and / or shortened battery life. Given that start / stop batteries and / or other enhanced flooded lead-acid batteries are expected to become increasingly prevalent in hybrid and all-electric vehicles to improve vehicle fuel efficiency and reduce CO2 emissions, solutions to reduce acid stratification and / or improve acid mixing are highly desirable.

[0014] In some cases, acid stratification can be avoided by using VRLA (valve regulated lead acid) technology, in which the acid is immobilized by a gel electrolyte and / or by an absorbed glass mat (AGM) battery separator system. In contrast to the free fluid electrolyte in flooded lead acid batteries, in VRLA AGM batteries, the electrolyte is absorbed on fibers or fibrous materials, such as glass fiber mats, polymer fiber mats, gel electrolytes, etc. However, VRLA AGM battery systems are much more expensive to manufacture than flooded battery systems. In some cases, VRLA AGM technology may be more sensitive to overcharge, may dry out at high temperatures, may experience a gradual decline in capacity, and may have a lower specific energy. Likewise, in some cases, gel VRLA technology may have a higher internal resistance and may have reduced charge acceptance.

[0015] Therefore, there is a need to further develop enhanced flooded lead-acid batteries, such as enhanced flooded start / stop batteries, that do not experience acid stratification when in use and / or that exhibit a reduced or significantly reduced degree of acid stratification when in use. A need exists for improved enhanced flooded lead-acid batteries that have improved uniformity and performance over previously available batteries and that have performance that may be comparable to or even exceed that of certain VRLA AGM batteries.

[0016] Battery separators are 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 between the positive and negative electrodes or plates. The separator can be made of polyolefins (e.g., polyethylene and polypropylene), wood, paper, rubber, PVC, and fiberglass. In lead-acid batteries, such as automotive batteries and / or industrial batteries and / or deep cycle batteries, the battery separator is usually a microporous polyethylene separator; in some cases, such a separator may include a back web and a plurality of ribs standing on one or both sides of the back web. See: Besenhard, JO edited Handbook of Battery Materials, Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), Chapter 9, pages 245-292. Some separators for automotive batteries are made into continuous lengths and rolled up, then folded and sealed along the edge (or a specific edge) to form a pouch or package or sleeve or pocket for accommodating electrodes for the battery. Certain separators, such as those used in industrial (or traction or deep cycle storage) batteries, are cut to approximately the same size as the electrode plates (sheets or leaves).

[0017] Separators made of polyolefins (such as polyethylene) typically contain silicon dioxide to promote wetting of the separator with a hydrophilic electrolyte. In some cases, a hydrophilic material (such as a glass liner) is attached to the separator to help wet and retain the active material coated on the positive electrode.

[0018] The electrodes in lead-acid batteries are usually made of lead alloys with a relatively high antimony content. The lead / antimony alloy has advantages both during the manufacture of the electrode frame and during the use of the battery (for the former, by way of example only, improved flow characteristics of the molten metal in the mold, higher hardness of the cast electrode frame, etc.); in particular, under cyclic loading, it ensures good contact between the terminal and the active material at the positive electrode, in addition to ensuring mechanical stability, thereby avoiding premature decline in capacity (the "antimony-free" effect) and providing improved cyclability. In addition, for deep-cycle batteries, antimony is usually present in the positive grid of the battery.

[0019] However, a disadvantage of antimony-containing positive electrodes is that the antimony may be dissolved in the electrolyte in ionic form and then migrate through the separator. Since antimony is more stable than lead, it can be deposited on the negative electrode. This process is described as antimony poisoning. By reducing the overvoltage of hydrogen, antimony poisoning leads to increased water consumption and therefore the battery requires more maintenance. In particular, antimony can catalyze the decomposition of water, reducing the charging voltage and increasing the energy required to fill the battery again, since water decomposition may consume some of the energy required to fill the battery again. Attempts have been made to completely or partially replace the antimony in lead alloys with other alloy components, but this has not produced satisfactory results. In summary, the presence of antimony in the positive grid of deep-cycle batteries may be a source of reduced cycle life.

[0020] U.S. Patent No. 5,221,587, the entire contents of which are incorporated herein by reference, discloses a battery separator comprising plastic and rubber. The rubber was found to retard the rate of antimony poisoning. U.S. Patent No. 5,221,587 discloses coating or incorporating rubber on or in a sheet.

[0021] For at least certain applications or batteries, there remains a need for improved separators that provide improved cycle life, reduced antimony poisoning, reduced water loss, reduced float current and / or reduced voltage required to fully charge the battery. More specifically, there remains a need for improved separators and improved batteries (e.g., golf carts or golf cart batteries) containing improved separators that provide improved battery life, reduced battery failure, 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 (e.g., a deep cycle battery), minimized increase in internal resistance, reduced resistance, increased wettability, reduced electrolyte soaking time, reduced battery formation time, reduced antimony poisoning, reduced acid stratification, improved acid diffusion and / or improved uniformity in lead-acid batteries.

[0022] In an EFB system, the electrodes are made of lead alloy. During the manufacturing process of such an EFB, a paste is applied to a grid and cured to form an electrode. The paste may contain one or more of carbon black, barium sulfate, lignin sulfonate, sulfuric acid, and water. The curing process changes the paste into a mixture of lead sulfate, which becomes an electrochemically active material when the battery is initially charged. The paste on the positive electrode is called the positive active material ("PAM"). Similarly, the active material on the negative electrode is called the negative active material ("NAM"). During the charge and discharge cycles of the battery, the electrodes undergo expansion and contraction. Over time, the deformation of the electrode causes the active material to fall off and physically separate from the electrode. As more and more active material falls off from the electrode, the efficiency of the electrode decreases, and the performance and life of the battery also decrease. Therefore, new battery separators and / or battery technologies are needed to meet and overcome the challenges posed by current lead-acid battery systems, especially to prevent or prevent the active material from falling off from the electrode in enhanced flooded lead-acid batteries. Summary of the invention

[0023] The details of one or more embodiments are set forth in the following description. Other features, objects, and advantages will be apparent from the description and claims. According to at least selected embodiments, the present disclosure or invention may address the above-mentioned problems or needs. According to at least certain objects, aspects, or embodiments, the present disclosure or invention may provide an improved separator and / or battery capable of overcoming the above-mentioned problems, such as by providing a battery having improved retention of active material on an electrode, in a particular embodiment, such improved retention of active material is provided by an improved separator comprising an improved retention liner, such as an improved PAM retention liner. Although the specific embodiments disclosed herein are directed to lead-acid battery separators for retaining PAM, they may also be used to retain NAM.

[0024] One embodiment of the present invention provides a lead-acid battery separator having a porous membrane, wherein the membrane or mesh has a plurality of ribs thereon. The ribs may be located on one or both of the surface facing the positive electrode and the surface facing the negative electrode. The separator of the present invention is also provided with a fiber mat on the surface facing the positive electrode.

[0025] According to at least selected embodiments, aspects, or purposes, the present disclosure or invention is directed to or may provide new or improved separators, battery separators, flooded battery separators, enhanced flooded battery separators, fiber mats, batteries, galvanic cells, and / or methods of making and / or using such separators, battery separators, fiber mats, enhanced flooded battery separators, galvanic cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead-acid battery separators for starter lighting ignition ("SLI") batteries, fiber mats, flooded batteries for deep cycle applications, and / or enhanced flooded batteries and / or systems, vehicles, and / or the like including such separators, mats, or batteries, and / or improved methods of making and / or using such improved separators, mats, galvanic cells, batteries, systems, vehicles, and / or the like. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries and / or improved methods of making and / or using such batteries having such improved separators. According to at least selected embodiments, the present disclosure or invention is directed to a separator, a flooded battery separator, preferably or particularly a separator for an enhanced flooded battery, which has reduced resistance and / or increased cold cranking current. In addition, methods, systems and battery separators for improving battery life, reducing water loss, reducing internal resistance, increasing wettability, reducing acid stratification, improving acid diffusion, improving cold cranking current and / or improving uniformity at least in an enhanced flooded battery are disclosed herein. According to at least particular embodiments, the present disclosure or invention is directed to an improved separator for an enhanced flooded battery, wherein the separator includes one or more performance enhancing additives or coatings, increased porosity, increased void volume, amorphous silica, silica with higher oil absorption, silica with more silanol groups, retention and / or improved retention of active materials on electrodes and / or any combination thereof.

[0026] According to at least certain embodiments, the present disclosure or invention is directed to improved flooded lead-acid batteries, improved battery separators, gaskets, composite separators, laminated separators, positive electrode packaging, negative electrode packaging and / or the like for such batteries, and / or methods of making, testing or using such improved flooded lead-acid batteries, or combinations thereof.

[0027] According to at least certain embodiments, aspects and / or objectives, the present invention, application or disclosure may provide solutions, new products, improved products, new methods and / or improved methods, and / or may address difficulties, needs and / or problems with PAM shedding, NAM shedding, electrode deformation, active material shedding, active material loss and / or physical separation, electrode efficiency, battery performance, battery life and / or cycle life, and / or may provide new battery separators, new battery technologies and / or new battery methods and / or systems that address the challenges posed by current lead-acid batteries or battery systems, particularly new battery separators, new battery technologies and / or new battery methods and / or systems that are suitable for preventing or inhibiting active material shedding from electrodes in enhanced flooded lead-acid batteries or in other batteries such as other flooded batteries, AGM batteries, partial state of charge (PSoC) batteries, ISS batteries, energy storage system (ESS) batteries or the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1A and Figure 1B is a photograph of an exemplary fiber mat as described in the present disclosure. Figure 1C and Figure 1D yes Figure 1A and Figure 1B A higher resolution photo of the padding in Figure 1D It is taken at an oblique angle to the pad which is lying flat. Figure 1E SEM images at low magnification are shown comparing an exemplary fiber mat to a conventional glass mat. Figure 1F-1H is a SEM image of an exemplary fiber mat as described in the present disclosure.

[0029] Figure 2A and Figure 2B is an illustration of a flooded lead-acid battery incorporating an exemplary embodiment of a separator assembly having an exemplary fiber mat.

[0030] Figure 3A-Figure 3F Variations of interrupted rib patterns are depicted in accordance with exemplary embodiments of the present disclosure.

[0031] Figure 4A-4G A battery separator having interrupted ribs according to an exemplary embodiment of the present disclosure and as defined in the pattern shown therein is shown.

[0032] Figure 5A A separator having three different areas of interrupted rib patterns is detailed. Figure 5B A variation of the interrupted ribs for a three-zone interrupted rib diaphragm is depicted. Figure 5C Depicted are variations of interrupted ribs for single-zone interrupted rib diaphragms.

[0033] Figure 6A-6HVariations of single-zone and multi-zone interrupted rib style partitions are depicted.

[0034] Figure 7 An exemplary spacer according to the invention is depicted having a discontinuous rib pattern, which may be placed, for example, between a flat separator and an electrode or gasket.

[0035] Figure 8 and Fig. 9 A configuration prototype of an exemplary inventive acid mixing configuration is depicted.

[0036] Fig.10 Exemplary embodiments of ribs having one or two tapered longitudinal ends, or ribs, serrated or interrupted ribs, or angled serrated or interrupted ribs having a particular end face angle (or angles within a particular range of angles) are depicted.

[0037] Fig.11A , Fig. 11B , Fig. 11C Depicted are exemplary embodiments of a separator having one or more ribs having one or more tapered longitudinal ends at a particular angle (or angle within a particularly preferred range). For example, Fig.10 , Fig.11A , Fig. 11B , Fig. 11C , Fig. 12A , Fig. 12B The stripe pattern separator layer shown in provides a flooded lead-acid battery (e.g., an enhanced flooded lead-acid battery) with a large amount of acid mixing (e.g., acid turbulence, reduced acid stratification, etc.). In addition, for example Fig.10 , Fig.11A , Fig. 11B , Fig. 11C , Fig. 12A , Fig. 12B The angular design of the separators shown in enables optimal surface area, optimal mixing, and optimal manufacturability and / or processability and / or packageability of the separator layers, particularly in view of the improvement in the stiffness ratio between the stiffness in the MD (machine direction) and the stiffness in the cross-machine direction (CMD). In addition, Fig.10 , Fig.11A , Fig. 11B , Fig. 11C , Fig. 12A , Fig. 12B The patterned separator layer shown in can be a separator layer that is stronger, or even significantly stronger, than conventional microporous separator layers.

[0038] Fig. 12A and 12B Two exemplary embodiments of separator layers are depicted, Fig. 12A The separator layer A is depicted, and Fig. 12BA separator layer B is depicted, both of which are based on various embodiments of the present disclosure, and are microporous membranes manufactured to have one or more intermittent rib patterns thereon, and the separator layer B has one or more ribs having one or more tapered longitudinal ends at a specific angle (or at an angle within a particularly preferred range).

[0039] Fig.13A is a top view of an exemplary battery separator positioned between the positive and negative electrodes, such as would be found in a typical lead-acid battery. Fig. 13B is a top view of an exemplary battery separator and swollen negative active material, as would be found in a typical lead-acid battery. Fig. 13C is a top view of an exemplary embodiment of a new or improved battery separator of the present invention disposed between a positive electrode and a negative electrode (such as those found in a typical lead-acid battery, a flooded battery, or an enhanced flooded battery); the negative electrode is shown with a swollen NAM (such as Fig. 13B As shown, it preferably does not contact or deflect the back web).

[0040] Fig.14 An exemplary embodiment of a rib profile for an exemplary embodiment of a separator of the present invention is shown. DETAILED DESCRIPTION

[0041] Now refer to Figure 1A and 1B , which shows a photograph of an exemplary embodiment of a fiber mat. Figure 1C and 1D is a higher resolution photograph of an exemplary embodiment of a fiber mat. The fiber mat can be a nonwoven, fleece, mesh, or any combination of layers thereof. The fiber mat can be a single layer, double layer, or other multi-layer mat. An exemplary nonwoven mat can have a thickness of about 100 μm to about 900 μm, and preferably in the range of about 200 μm to about 450 μm. Figure 1C and 1D A pattern of bundled fibers is shown. This can be done during formation of the pad and as the fiber-carrying liquid is drained, the fibers can collect at specific low points in the drainage network. Additionally, the pad can have combed fibers.

[0042] Preferred fiber mat components can be, for example, glass fibers, synthetic fibers, or any combination thereof. An exemplary embodiment of a fiber mat can be one that contains 5% to 25% synthetic fibers, with the remainder being glass and / or binder. However, the mat can be entirely glass or entirely synthetic. Examples of such synthetic fibers can be polypropylene, polyester [e.g., polyethylene terephthalate ("PET")], acrylic, other plastics, or any combination thereof. Additionally, the fiber component can be a polymer, homopolymer, or copolymer, or a fiber blend consisting of these components. Regardless of the composition of the fiber mat, it is preferred that it be resistant to the acid electrolyte of a lead-acid battery. These materials tend to be hydrophobic, so can result in gas entrapment. Therefore, a surfactant coating as generally described herein can be added.

[0043] The fiber mat may further have a filler, such as particulate silica, to increase surface area and reduce pore size. The fiber mat composition may further contain soluble fibers. The fiber mat may also include a gelling agent to help resist acid stratification. Additionally, the fiber mat may include a wetting agent additive or coating as generally described below.

[0044] An exemplary fiber mat may have a density of about 1500 1 / m 2 s to about 2500l / m 2 Preferred air permeability within the s range.

[0045] Exemplary fiber mats may have pore sizes preferably less than about 4.0 μm to 5.0 μm (measured as effective diameter). The fiber mat pore size is preferably smaller than the particle size of the active material used on the associated electrode. Table 1 below summarizes the pore sizes (μm) of fiber mats according to the present invention. 2 ) and the aperture of conventional glass liner (mm 2 ) for comparison.

[0046] Table 1

[0047] Exemplary fiber mats of the present invention Conventional glass liner average value <![CDATA[1332.65μm 2 ]]> <![CDATA[6896.95μm 2 ]]> Standard Deviation <![CDATA[1573.57μm 2 ]]> <![CDATA[6461.03μm 2 ]]> Sample size 63 29

[0048] An exemplary fiber mat may have a strength of about 6 mΩ·cm 2 to about 14 mΩ·cm 2 The preferred resistance range is preferably less than 14 or less than 13 or less than 12 or less than 11 mΩ·cm 2 .

[0049] An exemplary fiber mat may have a thickness of about 50 g / m 2 About 100g / m 2 The preferred area weight or basis weight is in the range of 50 g / m 2 About 65g / m 2 .

[0050] Exemplary fiber mats may have a preferred binder content ranging from about 15 wt % to about 21 wt %.

[0051] An 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.

[0052] In addition, the fiber can be solid or hollow, and the cross-sectional shape of the fiber can be circular, perfectly circular, oval or oblong, kidney-shaped, dog-bone-shaped, racetrack-shaped, polygonal or any combination thereof. In addition, exemplary fibers can have multiple parts, which are side-by-side configurations, shell-core configurations or island-in-the-sea configurations. In addition, the shell-core configuration can adopt any of the above shapes, and the core can be central or eccentric.

[0053] Now go to Figure 1E , which shows four SEM images at low magnification taken from two separate locations of an exemplary fiber mat and two separate locations of a conventional glass mat. The images show that the exemplary fiber mat has a more densely packed fiber network than the conventional glass mat. In addition, the fibers and open areas of the exemplary fiber mat are smaller than those of the conventional glass mat.

[0054] exist Figure 1F In this example, SEM images were taken from samples at two separate locations, and then two separate regions were obtained from each sample location. This was done to avoid any regional bias. Figure 1E Taken at a higher magnification. These images further show the packing density of the fibers and also show some fiber bundles, which may be due to the binder used and its content. The fiber mats that can be used in the various embodiments described herein may include bundles or bundles of fibers, such as bundles or bundles of glass fibers and / or synthetic fibers. In a specific embodiment, such bundles or bundles may be twisted before the fibers are bonded together. In such an embodiment, the twisting can be performed and an adhesive can be applied to fix the twisted fibers in place. In such an embodiment, a separator comprising a fiber mat containing fiber bundles or fiber bundles may exhibit increased strength compared to a separator comprising a conventional mat; similarly, in the case where the fibers are twisted, this separator comprising such a fiber mat may exhibit an even more significant increase in strength compared to a separator comprising a conventional mat. When such a fiber mat is manufactured using a wet-laid process according to the various preferred embodiments defined herein, a composite fiber bundle can be produced, wherein such a composite fiber bundle includes glass fibers and synthetic polymer fibers, for example, polyester fibers or PET fibers.

[0055] An exemplary fiber mat may have a synthetic fiber diameter of about 7.2 μm (± 0.5 μm) with a confidence interval of ± 95%. Table 2 below compares the fiber diameter (μm) of a fiber mat according to the present invention with the fiber diameter of a conventional glass mat.

[0056] Table 2

[0057] Exemplary fiber mats of the present invention Conventional glass liner average value 7.2408μm 13.83μm Standard Deviation 1.9741μm 1.2103μm Sample size 66 37

[0058] In addition, the fiber mat can be formed into bundles of fibers before or during the formation of the pad. The fiber bundle can be combed or twisted from multiple fibers having different material compositions, different cross-sectional shapes, different fiber diameters, and any combination thereof. The bundle can be laid in a patterned orientation, randomly placed, or a combination thereof. The bundled fibers can be laid on and / or within a randomly laid nonwoven or fiber pad layer. Thus, the resulting fiber mat can have a corrugated surface or a non-corrugated surface, or a combination thereof. Figure 1C and 1D is a photograph of an exemplary fiber mat having a corrugated surface. Bundles can also be formed during the production of the mat. Bundles can be formed simply by the contours of the carrier wire or surface used in the production of the mat. In addition, the mat can be laid up in two separate processes. For example, bundles can be formed with a non-water soluble binder and then a second layer of nonwoven fibers can be laid down to secure the fibers together. Bundles can be placed on either or both surfaces of the mat.

[0059] Figure 1G An image is shown for measuring fiber diameter of an exemplary fiber mat as it is measured by the linear distance of each fiber, fibers in a bundle are not measured, and two diameters are taken for each fiber measured (if possible). Figure 1G The data are shown in Table 1 above. Figure 1H is an image used to measure the pore size of the fiber mat. Figure 1H The data are shown in Table 2 above.

[0060] An exemplary flooded lead-acid battery may generally consist of one or more primary cells, each of which generally has one or more positive and negative electrodes. The electrodes may be configured as cast or stamped plates or grids. The electrodes may even be configured as cylinders or tubes. Each positive and negative electrode is further separated by a separator. In the present disclosure, a separator and a fiber mat are inserted between each electrode. As an example, Figure 2A A battery 100 is depicted having a single primary cell and a single negative electrode 102a and a single positive electrode 104a. However, it should be understood that a typical lead-acid battery contains multiple electrodes with an alternating series of positive and negative electrodes. Negative electrode 102a is electrically coupled to a negative battery terminal or post 102b. Likewise, positive electrode 104a is electrically coupled to a positive battery terminal or post 104b. In addition to having two negative electrodes 202a, Figure 2Band Figure 2A 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.

[0061] Go to Figure 2A , which shows an exemplary flooded lead-acid battery 100 having a single negative electrode 102a and a single positive electrode 104a, each electrode being electrically coupled to a negative terminal or post 102b and a positive terminal or post 104b, respectively. The terminals 102b, 104b are disposed on an outer surface of the battery 100 and generally extend from the top of the battery 100. It should be understood that a typical flooded lead-acid battery 100 will have more than two electrodes. However, for simplicity, only two are shown in this example. The exemplary battery 100 is also provided with and substantially filled with an electrolyte 101, with the dashed line representing the fill line of the electrolyte 101. In an exemplary embodiment, the electrode and separator assembly are substantially immersed in the electrolyte. The electrolyte 101 is typically sulfuric acid (H2SO4), having a specific gravity between about 1.20-1.30, preferably between about 1.26-1.28. It should be understood that any preferred specific gravity range depends on the application of the battery.

[0062] Continue watching Figure 2A , an exemplary separator assembly is disposed between the electrodes and is configured with a separator layer 106 (e.g., a microporous membrane separator layer) and an exemplary fiber mat 108, wherein 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 be collectively referred to as a separator assembly, but it should be understood that they may be connected / laminated or not connected / laminated together. It should also be understood that the fiber mat 108 may not be connected to anything, or may be attached or mounted to the electrode on the outer surface of the active material, or may be incorporated into a sticker applied to the electrode, or may be pressed in some way onto the electrode active material, or any combination thereof. It should be further understood that the fiber mat 108 may alternatively be disposed between the negative electrode 102a and the separator layer 106, or there may be a fiber mat on both sides of the separator layer 106. It is contemplated by the inventors that, regardless of whether the active material is a PAM or a NAM, the fiber mat will prevent or slow down the process of the active material falling off or separating from the electrode adjacent thereto.

[0063] like Figure 2AAs shown, the separator layer 106 and the fiber mat 108 can be arranged as leaves interlaced between the electrodes. The lateral and longitudinal dimensions of the separator layer 106 are preferably greater than the lateral and longitudinal dimensions of the electrodes 102a, 104a (i.e., the separator layer 106 is wider and taller than the electrodes 102a, 104a). The fiber mat 108 can extend from the side end to the side end of the separator layer 106, or from the end rib to the end rib (ribs not shown). In addition, the separator layer 106 can be simply flat without ribs, or can be embossed.

[0064] Go to Figure 2B , which shows an exemplary flooded lead-acid battery 200 having two negative electrodes 202a and a single positive electrode 204a disposed therebetween, each electrode being electrically coupled to a negative terminal or post 202b and a positive terminal post 204b, respectively. It should be understood that a typical flooded lead-acid battery will have more than three electrodes. However, for simplicity, only three are shown in this example. The exemplary flooded lead-acid battery 200 is further provided with and substantially filled with an electrolyte 201 as generally described herein. The dashed line represents the fill line of the electrolyte 201, in which the electrode and separator assembly is substantially immersed.

[0065] Continue watching Figure 2B , which shows an exemplary separator assembly including an encapsulated separator layer 206 and an encapsulated fiber mat 208, which encapsulates the positive electrode 204a, and the separator layer 206 wraps the fiber mat 208. The separator layer 206 is preferably adjacent to both negative electrodes 202a, and the fiber mat 208 is preferably adjacent to the positive electrode 204a and between the separator layer 206 and the positive electrode 204a. It should be understood that the separator layer 206 and the fiber mat 208 can be connected / laminated or not connected / laminated together as a unit. It should be further understood that the fiber mat 208 may not be connected to anything, or may be attached or mounted to the electrode on the outer surface of the active material, or incorporated into a sticker applied to the electrode. It should also be understood that the fiber mat 208 may be alternatively disposed between the negative electrode 202a and the separator layer 206, wherein the fiber mat 208 wraps the separator layer 206. Fiber mats may also be present on both sides of the separator layer 206. It is contemplated by the inventors that, regardless of whether the active material is a PAM or a NAM, the fiber mat will prevent or slow down the process of the active material falling off or separating from the electrode adjacent thereto.

[0066] As described above, the exemplary separator assembly including the separator layer 206 and the fiber mat 208 combination can be packaged. The sides of the combination can be sealed together into a continuous or intermittent seam. Such sealing methods are well known to those skilled in the art. In addition, the bottom pleat of the package can be closed or have one or more openings with a length less than the width of the package. The fiber mat 208 can extend from side end to side end of the separator layer 206, or from end rib to end rib (ribs not shown). In addition, the package separator layer 206 can be simply flat without ribs.

[0067] Some other exemplary embodiments of separator assembly configurations include: negative or positive packaging, negative or positive enclosure, negative or positive hybrid packaging (variations on standard packaging), both plates can be packaged or encapsulated, and any combination thereof. In addition, various separators of the present disclosure may include a separator layer (e.g., separator layer 106), a fiber mat (e.g., fiber mat 108), and a glass liner (not shown).

[0068] The fiber mat 108, 208 may simply be disposed adjacent to the separator layer 106, 206, or it may be connected, attached or laminated to the separator layer 106, 206 in some manner. Several methods of attaching the fiber mat 108, 208 to the separator layer 106, 206 are known to those skilled in the art. The method may include, for example, bonding the different layers together by adhesive, ultrasonic welding or sealing or ultrasonic stitching. An adhesive such as an acrylate or polyethylene hot melt is preferably used to improve the bonding between the microporous polymer layer and the fiber layer. The adhesive is preferably applied between the layers of the separator in the form of separate dots or continuous strips. If the separator layer 106 and the fiber mat 108 are laminated together, the ribs (not shown) can be spaced farther apart than the separator layer not laminated with the fiber mat, because the fiber mat will provide additional support for the separator layer, thereby providing more space for the electrolyte. However, the separator layer 106 and the fiber mat 108 do not need to be laminated together, but can simply be disposed adjacent to each other.

[0069] The separator of the present invention preferably comprises a porous membrane (such as a microporous membrane having pores less than about 1 micron, a mesoporous or macroporous membrane having pores greater than about 1 micron), which is made of a natural or synthetic material, such as polyolefins, polyethylene, polypropylene, phenolic resins, natural or synthetic rubber, latex, synthetic wood pulp (SWP), glass fiber, synthetic fiber, cellulose fiber or a combination thereof, and a more preferred separator embodiment comprises a microporous membrane made of a thermoplastic polymer. The preferred microporous membrane may have a pore size of about 0.1 micron (100 nanometers) and a porosity of about 60%. In principle, thermoplastic polymers may include all acid-resistant thermoplastic materials suitable for lead-acid batteries. Preferred thermoplastic polymers include polyethylene compounds and polyolefins. Polyethylene compounds include, for example, polyvinyl chloride (PVC). Polyolefins include, for example, polyethylene, which includes ultra-high molecular weight polyethylene (UHMWPE) and polypropylene. A preferred embodiment may include UHMWPE and fillers (such as silica). Typically, the preferred films can be prepared by mixing fillers, thermoplastic polymers such as UHMWPE, latex and / or rubber (if desired) and processing plasticizers (eg, processing oils) in an extruder.

[0070] The microporous membrane layer may include a polyolefin, such as polypropylene, ethylene-butene copolymer, and preferably polyethylene, more preferably high molecular weight polyethylene (e.g., polyethylene having a molecular weight of at least 600,000), and even more preferably ultra-high molecular weight polyethylene (e.g., polyethylene having a molecular weight of at least 1,000,000, especially greater than 4,000,000, and most preferably 5,000,000 to 8,000,000 (as measured by a viscometer and calculated by the Margolie equation)), a standard load melt index of substantially zero (0) (measured as specified in ASTM D 1238 (Condition E) using a standard load of 2,160 g), and a viscosity value of not less than 600 ml / g, preferably not less than 1,000 ml / g, more preferably not less than 2,000 ml, and most preferably not less than 3,000 ml / g (as measured at 130° C. in a solution of 0.02 g of polyolefin in 100 g of decalin).

[0071] In certain selected embodiments, the membrane may be prepared by mixing about 5-15% polymer (in some cases, about 10% polymer), about 10-75% filler (in some cases, about 30% filler) and about 10-85% process oil (in some cases, about 60% process oil) by weight. In other embodiments, the filler content is reduced and the oil content is higher, for example, greater than about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70% by weight. The filler: polymer ratio (by weight) may be about (or may be between these specific ranges) such as 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1 or 6:1. The filler: polymer ratio (by weight) can be from about 1.5: 1 to about 6: 1, in some cases from 2: 1 to 6: 1, from about 2: 1 to 5: 1, from about 2: 1 to 4: 1, and in some cases from about 2: 1 to about 3: 1. The amounts of filler, oil, polymer (e.g., polyethylene), and rubber and / or latex (if desired) are balanced based on performance and desired separator properties (e.g., electrical resistance (ER), porosity, physical strength, tortuosity, etc.).

[0072] According to at least one embodiment, the porous membrane may include ultra-high molecular weight polyethylene (UHMWPE) mixed with processing oil and precipitated silica. According to at least one embodiment, the microporous membrane may include ultra-high molecular weight polyethylene (UHMWPE) mixed with processing oil, additives and precipitated silica. The mixture may also include a small amount of other additives or reagents common in the field of separators (e.g., wetting agents, colorants, antistatic additives and / or the like). In certain cases, the microporous polymer layer can be a uniform mixture of 8 to 100% by volume of polyolefin, 0 to 40% by volume of plasticizer and 0 to 92% by volume of inert filler material. The filler can be dry finely divided silica. The preferred plasticizer is petroleum. Since the plasticizer is the component that is most easily removed from the polymer-filler-plasticizer composition, it is useful for imparting porosity to the battery separator.

[0073] In some embodiments, porous membrane can be prepared by mixing about 30% by weight of silica and about 10% by weight of UHMWPE and about 60% of processing oil in an extruder. The preparation steps of microporous membrane are as follows: the components are passed through a heated extruder, the extruded profile produced by the extruder is passed through a die into a clamp formed by two heated calendering rollers to form a continuous web, a large amount of processing oil is extracted from the web by using a solvent, the web after extraction is dried, the web is cut into strips of a predetermined width, and the strips are rolled into rolls. The calendering roller can be engraved with various groove patterns to give film ribs, sawtooth, embossing, etc. Alternatively or in addition thereto, ribs, etc. can be given to porous membrane by passing the extruded film through an additional calendering or embossing roller or press of an appropriate groove.

[0074] Suitable fillers include silica, alumina, talc and / or combinations thereof. When forming a lead-acid battery separator of the type shown herein, silica having a relatively high level of oil absorption and a relatively high level of affinity for mineral oil becomes dispersed in a mixture of polyolefins (e.g., polyethylene) and mineral oil as desired. In addition, the silica used here can be precipitated silica and / or amorphous silica. In some selected embodiments, the average particle size of the filler is no greater than 25 μm, and in some cases, no greater than 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm. In some cases, the average particle size of the filler particles (e.g., silica) is 15-25 μm. The particle size of the silica filler can affect the oil absorption of the silica and / or the surface area of ​​the silica filler. The silica particles in the finished product or separator can fall within the above-mentioned size. However, the initial silica used as a raw material can be one or more aggregates and / or agglomerates, which can have a size of about 200 μm or more. In certain embodiments, the finished separator sheet has a residual or final oil content in the range of about 0.5% to about 40% per unit weight of the separator sheet product, in certain embodiments, about 10 to about 30% residual process oil, and in some cases, about 20 to about 30% residual process oil or residual oil. As for the pore size of the separator membrane (if necessary, in certain embodiments, comprising polyolefins, such as polyethylene, and latex and / or rubber), the pore size can be submicron up to 100 μm, and in specific embodiments, between about 0.1 μm and about 10 μm. In specific embodiments, the separator membrane may have an average porosity greater than about 10% and less than about 90%, and in other embodiments, the porosity may be greater than about 40% and less than about 80%. In certain selected embodiments, the separator membrane may have a porosity greater than about 50%, in other embodiments, the porosity may be greater than about 60%, in specific embodiments greater than about 65%, and in specific other embodiments greater than about 70%. Preferred embodiments provide a porous membrane with a porosity greater than at least about 64%.

[0075] The microporous membranes made according to the present invention, comprising polyethylene, fillers (such as silica) and latex and / or rubber, typically have a residual oil content; in certain embodiments, such residual oil content is from about 0.5% to about 40% of the total weight of the separator membrane (in some cases, about 10-30% of the total weight of the separator membrane, and in some cases, about 20-30% of the total weight). In certain selected embodiments herein, part or all of the residual oil content in the separator can be replaced by adding more performance enhancing additives; the performance enhancing additives are, for example, surfactants, surfactants with an HLB of less than 6, or, for example, nonionic surfactants. For example, performance enhancing additives such as surfactants, such as nonionic surfactants, can constitute from 0.5% to all (e.g., up to 20 or 30 or even 40%) of the residual oil content in the total weight of the microporous separator membrane, thereby partially or completely replacing the residual oil in the separator membrane.

[0076] The separator disclosed herein contains latex and / or rubber, which can be natural rubber, synthetic rubber or a mixture thereof. The natural rubber can include a blend of one or more polyisoprenes, which can be purchased from multiple suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, brominated butyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber and silicone rubber and copolymer rubbers, such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM) and ethylene / vinyl acetate rubber. The rubber can be a crosslinked rubber or a non-crosslinked rubber; in a specific preferred embodiment, the rubber is a non-crosslinked rubber. In a specific embodiment, the rubber can be a blend of crosslinked and non-crosslinked rubbers. The rubber may be present in the separator in an amount of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight relative to the weight of the finished separator (the weight of the polyolefin separator sheet or layer containing rubber and / or latex). In certain embodiments, the rubber may be present in an amount of about 1-20%, 2-20%, 2.5-15%, 2.5-12.5%, 2.5-10% or 5-10% (by weight).

[0077] In order to make a separator based on the present invention, rubber and / or latex can be added to an extruder together with a polymer (e.g., polyethylene), a filler (e.g., silica), and a processing oil and / or a plasticizer. In other embodiments, a liquid slurry containing rubber and / or latex, optionally silica and water, can be coated on one or both sides of a microporous membrane (e.g., polyethylene film), preferably on the side facing the negative electrode, and then dried and / or formed into a film of such material on the surface of the microporous membrane (e.g., polyethylene film) therein. In order to make the wettability of this layer better, a known wetting agent used in lead-acid batteries can be added to the slurry. In a particular embodiment, the slurry may also contain one or more performance enhancing additives (e.g., surfactants) described in detail below. After drying, a porous layer and / or film is formed on the surface of the separator, which adheres well to the microporous membrane and, if it does exist, only insignificantly increases the resistance. After the rubber is added to obtain the separator, it can be further compacted with a press, a calender, or a roller. The separator may be provided with ribs, grooves, serrations, serrated ribs, embossing, and the like, using an engraving press or calendar.

[0078] Further embodiments of the present invention relate to depositing rubber onto the membrane by injection and drying. For this purpose, glass mats, fleece fabrics or fibers made of synthetic fibers or mixtures containing synthetic fibers (such as those described in the above-mentioned fiber mats) can be used as carrier materials. For example, the fiber mat can be a carrier for performance enhancing additives (such as antimony inhibition additives), and it can be injected into or contained in the fiber mat or 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 can contain rubber and / or latex, optional silica, water and / or one or more performance enhancing additives (such as various additives described herein), wherein in surface embodiments, a film of such material can be formed on one or more surfaces of the treated fiber mat. Adhesion can be carried out by extrusion or bonding.

[0079] In various embodiments of the present invention, the porous and / or microporous membrane contains a polyolefin (e.g., polyethylene), latex and / or rubber, a filler (e.g., silica), any residual oil and / or plasticizer, and a performance enhancing additive in the form of a coating (e.g., a surfactant coating) is laminated to another layer, such as the above-mentioned fiber mat or a fiber mat having enhanced capillary properties and / or enhanced electrolyte wetting or retention properties. Such a fiber mat has a thickness of at least about 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, and the like. The laminated separator can then be cut into sheets. In a specific embodiment, the fiber mat is laminated on the ribbed surface of the microporous membrane separator layer. In a specific embodiment, the improved separator described herein brings handling and / or assembly convenience to battery manufacturers because it can be supplied in the form of rolls or cut sheets. Also, as mentioned above, the improved separator may be a stand-alone separator sheet or layer without the addition of one or more fiber mats or retaining mats or the like.

[0080] In some embodiments, rubber and / or latex can be mixed with polymer, filler and processing oil (optionally with other additives), and extruded together to obtain a mixed separator. In this way, a uniform separator with rubber uniformly dispersed throughout the film can be obtained. In some embodiments, the porous membrane can be injected with rubber latex and then dried.

[0081] The mixture may also include small amounts of other additives or agents (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like), as is common in the separator field. The mixture is extruded into a flat sheet shape, or a sheet with ribs or other protrusions on one or both sides of the sheet. After the film is extruded, a mechanical press or calender stack or rollers may be used to further compress the film.

[0082] The ribs and / or the like may be imparted to the microporous membrane using an engraving press or calendar. The ribs may be uniform groups, alternating groups, or a mix or combination of: solid, discrete, intermittent ribs; continuous, discontinuous, angular, linear, longitudinal ribs extending substantially along the machine direction ("MD") of the separator (i.e., from the top to the bottom of the separator in the battery); side ribs extending substantially along the cross-machine direction ("CMD") of the separator; transverse ribs extending substantially along the cross-machine direction ("CMD") of the separator (i.e., the transverse direction of the separator in the battery, perpendicular to the MD); transverse ribs extending substantially along the cross-machine direction of the separator; discrete teeth or toothed ribs, serrations, serrated ribs, ridged protrusions or ridged ribs, arcuate or sinusoidal, arranged in a solid or intermittent zigzag manner, grooves, furrows, textured areas, embossings, depressions, pores, no pores, mini-ribs or cross-cut mini-ribs, and / or the like, and combinations thereof. Furthermore, any set of ribs may extend from or enter the positive electrode side, the negative electrode side, or both electrode sides.

[0083] In certain embodiments, the separator membrane may have a back web that is 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 thick (although in particular embodiments, very thin sheets having a thickness of less than 50 μm are provided, for example, between 10 μm and 50 μm in thickness). In particular embodiments, the porous membrane may have a backing web of about 50-1,000 μm, about 50-750 μm, about 100-750 μm, about 200-750 μm, about 200-500 μm, about 150-500 μm, about 250-500 μm, about 250-400 μm, or about 250-350 μm.

[0084] In various possible preferred embodiments, the porous membrane comprises ribs, such as serrated, reinforced, angular ribs, or discontinuous ribs, or combinations thereof. Preferred ribs may be 8 μm to 1 mm high and may be spaced 1 μm to 20 mm apart, and the preferred back web thickness of the microporous polyolefin separator layer (excluding ribs or embossing) may be about 0.05 mm to about 0.50 mm (e.g., in certain embodiments, about 0.25 mm). For example, the rib spacing may be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 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. In some embodiments, the ribs can form a pattern, for example, they can be located on one side of the separator layer or on both sides of the polyolefin separator, relative to each other at 0 ° -90 °. In some embodiments, the acid mixed ribs can be ribs on the front side, the positive electrode or the positive electrode side. Various patterns including ribs on both sides of the separator or separator layer may include positive electrode ribs on the second side or back of the separator and negative electrode longitudinal or transverse ribs, such as smaller, more closely spaced negative electrode longitudinal or transverse ribs or mini ribs. In some cases, the height of such negative electrode longitudinal or transverse ribs can be about 0.025mm to about 0.1mm, and preferably about 0.075mm high, but can be as high as 0.25mm. Other styles may include ribs on both sides of the separator layer and have negative electrode mini ribs on the second side or back of the separator (mini ribs extending in the same direction relative to the transverse direction compared to the main ribs on the other side of the separator). In some cases, the height of such negative mini-ribs may be from about 0.025 mm to about 0.25 mm, and preferably from about 0.050 mm to about 0.125 in height.

[0085] In certain preferred embodiments, the ribs may be serrated. The sawtooth 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 greater than or equal to 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0086] The average base length of the serrations or serrated ribs may be about 0.05 mm to about 1 mm. For example, the average base length may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0087] If serrations or serrated ribs are present, their average height may be from about 0.05 mm to about 4 mm. For example, the average height may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm. For embodiments where the height of the serrations is the same as the height of the ribs, the serrated ribs may also be referred to as protrusions. Such ranges may be applicable to separators for industrial traction start / stop batteries, where the total thickness of the separators may typically be from about 1 mm to about 4 mm, as well as automotive start / stop batteries, where the total thickness of the separators may be slightly less (e.g., typically from about 0.3 mm to about 1 mm).

[0088] The average center spacing of the serrations or serrated ribs may be about 0.1 mm to about 50 mm. For example, the average center spacing may be greater than or equal to about 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm; and / or less than or equal to about 1.5 mm, 1.25 mm, 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm.

[0089] The ratio of the average height to the base width of the serrations or sawtooth-like ribs may be from about 0.1: 1 to about 500: 1. For example, the ratio of the average height to the base width may be greater than or equal to about 0.1: 1, 25: 1, 50: 1, 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1, or 450: 1; and / or less than or equal to about 500: 1, 450: 1, 400: 1, 350: 1, 300: 1, 250: 1, 200: 1, 150: 1, 100: 1, 50: 1, or 25: 1.

[0090] The ratio of the average base width to the tip width of the saw teeth or saw-tooth-like ribs may be about 1000:1 to about 0.1:1. For example, the average base width to tip width ratio may be greater than or equal to about 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 or 1:1.

[0091] In certain embodiments, the separator may be recessed. Recesses are typically raised features or small pieces on one or more surfaces of the separator. The thickness of the recesses may be 1-99% of the thickness of the separator. For example, the average thickness of the recesses may 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 thickness of the separator. The recesses may be arranged in rows along the separator. The rows or columns may be spaced apart by about 1 μm to about 10 mm. For example, the rows can be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 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. In contrast, the depressions can be arranged in a random array or in a random manner.

[0092] The average depression length of the depression may be about 0.05 mm to about 1 mm. For example, the average depression length may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0093] The average depression width of the depressions may be about 0.01 mm to about 1.0 mm. For example, the average depression width may be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0094] The average center spacing of the depressions may be about 0.10 mm to about 50 mm. For example, the average center spacing may be greater than or equal to about 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm; and / or less than or equal to about 1.5 mm, 1.25 mm, 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm.

[0095] The shape of the depression can be a quadrilateral, such as a square and a rectangle. The ratio of the average depression length to the depression width of the depression can be about 0.1:1 to about 100:1. For example, the ratio of the average length to the bottom width can be greater than or equal to about 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 :1, and / or less than or equal to about 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 or 1:1.

[0096] In certain embodiments, the depressions can be substantially circular. The diameter of the circular depressions can be about 0.05 to about 1.0 mm. For example, the average depression diameter can be greater than or equal to about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm; and / or less than or equal to about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm.

[0097] Various other shapes for the depressions may also be included. By way of example only, such depressions may be triangular, pentagonal, hexagonal, heptagonal, octagonal, oval, elliptical, and combinations thereof.

[0098] In certain embodiments, the separator may be characterized by a combination of ribs, serrations or serrated ribs, depressions, or combinations thereof. For example, the separator may have a series of serrated ribs running from top to bottom along the separator, and a second series of serrated ribs running horizontally along the separator. In other embodiments, the separator may have an alternating sequence of serrated ribs, depressions, continuous, intermittent, or interrupted solid ribs, or combinations thereof.

[0099] Table 3 includes several specific embodiments of separators, provided by way of example only and not limitation, having serrations and / or depressions and various parameters that may be used to form such separators to prevent acid stratification and enhance acid mixing in flooded lead acid batteries (sometimes also referred to as enhanced flooded batteries).

[0100] Table 3

[0101]

[0102] Specific uses of various embodiments experience start / stop cycles, such as those used in vehicles. This means that the vehicle and its associated battery will have intervals of stopping while in motion, effectively shaking the battery. The separators disclosed herein preferably provide enhanced electrolyte mixing and / or acid circulation compared to conventional separators. In specific embodiments, the separator provides less acid stratification, as measured by the electrolyte density at the top and bottom of the battery. After the battery has been through 30, 60, 90 or more start / stop events or cycles, the density difference may be less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2.5% or 1%. In specific 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 battery has been kept stationary for 24, 48, 72 hours or more.

[0103] Now go to Figures 3A-3F , several exemplary embodiments depict arrangements of interrupted ribs with variables that define the pattern of interrupted ribs for various battery separator embodiments. Figures 4A-4G An exemplary embodiment according to the present disclosure is shown and Figures 3A-3F A battery separator having discontinuous ribs defined by a pattern or arrangement in FIG. An exemplary battery separator is shown in FIG. Figures 4A-4G In addition, the exemplary battery separator disclosed herein may have any number of columns 406, such as column 406 1 -406 n .

[0104] Figure 5AA separator is shown in detail having three regions with different interrupted rib patterns that vary in the transverse direction along the transverse process direction of the separator. It should be noted that the regions can also be spread in the process direction of the separator, or in both the process and transverse process directions of the separator. It should also be understood that there can be any number of regions in either direction or both directions. In addition, the edges of the separator can themselves be their own regions, so that the edges are optimized to have a particular design and / or ribbed pattern and / or interrupted rib pattern, etc., to obtain better results. In a specific preferred embodiment herein, the separator is formed (for a multi-region separator) with the following purpose: the quality of the pattern in each region is relatively consistent and / or the patterned separator performs well on the battery forming equipment and / or allows faster battery formation due to efficient acid filling.

[0105] Figure 5B Depicted are the intermittent rib pattern variations of the partitioning diaphragm. The subscript numbers "1" and "2" refer to two different intermittent rib patterns. In a particular embodiment, region 1 and region 3 (subscript "1") contain the same pattern, such as an intermittent rib pattern, and region 2 (subscript "2") has a pattern, such as an intermittent rib pattern, that is different from the pattern in regions 1 and 3. Figure 5C The interrupted rib variables for a single partitioned interrupted rib partition are depicted.

[0106] Figures 6A-6H Variations of zoned or multi-zone or tri-zone interrupted rib style partitions are depicted.

[0107] Figure 7 An exemplary inventive spacer 700 is depicted having a pattern of interrupted ribs 702 that may be placed between a separator and an electrode. As can be seen, the interrupted 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 should be understood that other angles may be incorporated.

[0108] Figure 8 and 9 Depicted are profile prototypes of exemplary inventive acid mixing profiles for various separator layers used herein.

[0109] The separator may include negative longitudinal ribs or cross-cutting ribs or mini-ribs, for example negative ribs having a height of about 25 to 250 microns, and may preferably be about 50 to 125 microns, and more preferably about 75 microns.

[0110] In certain embodiments, the protrusions may include ribs, wherein each rib has a longitudinal axis disposed at an angle of 0° to less than 180° relative to the top edge of the separator. In some cases, all of the ribs in the separator may be disposed at the same angle, while in other embodiments, there may be ribs disposed at different angles. For example, in certain embodiments, the separator may include multiple rows of ribs, wherein at least some of the rows have ribs disposed at an angle θ relative to the top edge of the separator. All of the ribs in a single row may have the same approximate angle, but in other cases, a single row may contain ribs at different angles.

[0111] In certain cases, the entire face of the separator will contain multiple rows of protrusions or intermittent ribs, while in other embodiments, specific segments of the separator face will not include protrusions or intermittent ribs. These segments can occur along any edge of the separator, including the top, bottom or sides, or can occur toward the middle of the separator, where the segment surrounds one or more sides having protrusions in part thereof.

[0112] Figure 8 A depiction of a separator 800 is included, the separator 800 includes a top edge 803, and a first row R1 and a second row R2. In a particular embodiment, the ribs 801 in the first row R1 are disposed at an angle θ1 of 0° to less than 180°, and the ribs 802 in the second row R2 are disposed at an angle θ2 of 0° to less than 180°, which may be the same or different than the angle of the ribs 801 in the first row R1. Although not shown, the angles θ1, θ2 may further vary across each individual rib 801, 802, respective row R1, R2. Additionally, groups of intermittent ribs may be easily patterned in columns.

[0113] Fig. 9 The diagram includes a depiction of a separator 900 including a top edge 901 having a first middle portion 902 and an outer second portion 903. In certain embodiments, the first middle portion 902 may include one or more rows. Fig. 9 As shown, the styles of the first row R1 and the second row R2 are similar to Figure 8 The style shown in: the ribs in the first row R1 are arranged at an angle of 0° to less than 180°, and the ribs in the second row R2 are arranged at an angle of 0° to less than 180°, which can be the same as or different from the angle of the ribs in the first row R1.

[0114] Continue watching Fig. 9, the outer second portion 903 may include a third row R3 having ribs at an angle θ3 relative to the top edge of the back web, wherein θ3 is 0° to 90°, 30° to 85°, 45° to 85°, 60° to 85°, 60° to 80° from 60° to 75°. A preferred value of θ3 is 90°. The outer second portion 903 may also include a fourth row R4 having ribs at an angle θ4 relative to the top edge of the back web, wherein θ4 is 90° to less than 180°, 95° to 150°, 95° to 120°, 100° to 120°, or 105° to 120°. A preferred value of θ4 is 90°. The ribs in different rows may have the same or different sizes as the ribs in other rows, and the ribs within a row may have the same or different sizes. The distance between adjacent rows may be -5mm to +5mm, where negative numbers indicate the degree of overlap of the rows. The distance can be measured from center rib to center rib.

[0115] When there are different rows, the rows can appear in a repeating pattern. The simplest repeating pattern -R3-R4- can be seen in 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-R3-R3-R3-R4-, -R3-R3-R3-R4-R4-, etc. In addition, groups of interrupted ribs can easily form patterns through the columns.

[0116] In certain selected embodiments, the porous separator may have longitudinal or transverse ribs of the negative electrode as protrusions on the opposite side of the membrane. The negative electrode ribs or the back ribs may be parallel to the top edge of the separator, or may be arranged at an angle thereto. For example, the transverse ribs may be oriented about 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15° or 5° relative to the top edge, and the transverse ribs may be oriented about 90-60°, 60-30°, 60-45°, 45-30° or 30-0° relative to the top edge. Typically, the transverse ribs are located on the face of the membrane facing the negative electrode. In certain embodiments of the invention, the ribbed film may 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 certain embodiments of the invention, the ribbed film may have a transverse cross-rib height of no greater than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0117] In certain embodiments of the invention, the ribbed film may 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 certain embodiments of the invention, the ribbed film may have a transverse cross-rib width of no more than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0118] In certain selected embodiments, the porous membrane may 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 certain embodiments, the porous membrane may 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.

[0119] Microporous membrane can have the back web thickness of at least 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1.0mm. Ribbed separator can have the back web thickness of not more than about 1.0mm, 0.9mm, 0.8mm, 0.7mm, 0.6mm, 0.5mm, 0.4mm, 0.3mm, 0.2mm or 0.1mm. In certain embodiments, microporous membrane can have the back web thickness between about 0.1-1.0mm, 0.1-0.8mm, 0.1-0.5mm, 0.1-0.5mm, 0.1-0.4mm, 0.1-0.3mm. In certain embodiments, microporous membrane can have the back web thickness of about 0.2mm.

[0120] Fig.10 A side profile of a separator 1000 is depicted having intermittent ribs 1004 extending outwardly from the surface of a porous membrane 1002 having tapered longitudinal ends 1006 identified by an angle θ.

[0121] Reference now Fig.13A, which shows an exemplary battery cell 1300 looking down from the top of an exemplary battery (the entire battery is not shown). The battery cell is equipped with an acidic electrolyte 1301, such as a sulfuric acid (H2SO4) electrolyte, which immerses the negative electrode 1302, the positive electrode 1304, and a separator assembly 1308 disposed between the electrodes 1302, 1304. The separator assembly 1306 can be provided with a porous membrane 1308 and a fiber mat 1310. The porous membrane 1308 can be provided with a series of positive electrode ribs 1308a extending therefrom and in contact with the fiber mat 1310. The fiber mat 1310 can be disposed in close contact with the positive electrode 1304. Although not shown, the porous membrane 1308 can be further provided with negative electrode ribs as described herein and in contact with the negative electrode 1302. The negative electrode 1302 can be provided with a negative active material ("NAM"), and the positive electrode 1304 can be provided with a positive active material ("PAM").

[0122] It is believed that in certain cells, the NAM may expand to the point where it exerts sufficient pressure on the porous membrane 1308 to cause it to deflect between the positive electrode ribs 1308a. Fig. 13B The cause and effect of this expansion and deflection is schematically shown, causing the porous membrane 1308 to contact the fiber mat 1310. When the porous membrane 1308 deflects enough, both the negative electrode 1302 and the positive electrode 1304 are starved of electrolyte (i.e., acid starved). This acid starvation negatively affects the performance of the battery and can be seen in deep cycle batteries and batteries operating in PSoC. Although not shown, the porous membrane 1308 can be further provided with negative electrode ribs and in contact with the negative electrode 1302 as described herein.

[0123] Reference now Fig. 13C , which shows a schematic diagram of an exemplary separator assembly 1306 of the present invention. In this embodiment, an array of positive ribs 1308a extending from the porous membrane 1308 in the machine direction and in contact with the fiber mat 1310 is provided. In addition, an array of negative ribs 1308b extending from the porous membrane 1308 in the machine direction and in contact with the negative electrode 1302 is provided. This provides spacing between the NAM and the backing mesh so that NAM expansion does not affect the porous membrane 1308. In addition, both the positive ribs 1308a and the negative ribs 1308b can be spaced closer than Fig. 13B Shown closer together to provide more support for NAM.

[0124] It should be noted that Figures 13A to 13C Not drawn to scale.

[0125] Reference now Fig.14, an exemplary porous membrane separator 1400 is provided with a backing web 1402 having positive electrode ribs 1404 extending therefrom and substantially aligned with the machine direction ("MD") of the separator, the ribs being used to contact the fiber mat ( Fig.14 1404). The separator is also provided with negative electrode ribs 1410, which are substantially consistent with the machine direction of the separator and substantially parallel to the positive electrode ribs 1404. The negative electrode ribs 1410 are used to contact the negative electrode in the exemplary battery. Although the direction of the negative electrode ribs 1410 in the illustrated example is substantially consistent with the machine direction of the separator, they may alternatively be substantially consistent with the cross-machine direction, generally referred to as negative electrode cross-cutting ribs.

[0126] Continue to refer Fig.14 , selected embodiments of the separator of the present invention are provided with an array of positive ribs 1404. The positive ribs 1404 are provided with a bottom 1406, which may extend the length of the separator in the machine direction. Then, spaced teeth, intermittent peaks or other protrusions 1408 may extend from the surface of the bottom 1406 so that the teeth 1408 are elevated above the lower surface of the porous membrane backing 1402. In addition, the bottom 1406 may be wider than the teeth 1408 themselves. The positive ribs 1404 are arranged substantially parallel to each other at a typical spacing of about 2.5 mm to about 6.0 mm, with a typical spacing of about 3.5 mm. The height of the positive ribs 1404 (the sum of the bottom 1406 and the teeth 1408) measured from the surface of the porous membrane backing 1402 may be from about 10 μm to about 4.0 mm, with a typical height of about 0.5 mm. Exemplary rib teeth 1408 of adjacent ribs 1404 may be substantially in line with each other. However, as Fig.14 As shown, the exemplary teeth 1408 can be offset from one rib 1404 to an adjacent rib 1404, or completely or partially different from adjacent ribs. As shown, the teeth 1408 are completely different from one rib 1404 to an adjacent rib. The positive rib teeth 1408 can be spaced apart in the machine direction of the separator at a spacing of about 3.0 mm to about 6.0 mm, with a typical spacing of about 4.5 mm.

[0127] like Fig.14 As shown in FIG, the negative electrode ribs are depicted as being substantially parallel to the machine direction of the separator. However, they may alternatively be substantially parallel to the cross-machine direction. The exemplary negative electrode ribs shown are shown as solid and substantially straight. However, they may alternatively be substantially parallel to the cross-machine direction. Fig.14 The negative ribs may be toothed in a similar manner to the positive ribs shown in . The negative ribs may be spaced at a pitch of about 10 μm to about 10.0 mm, with a preferred pitch between about 700 μm and about 800 μm, and a more preferred nominal pitch of about 740 μm. The height of the negative ribs measured from the surface of the back web may be about 10 μm to about 2.0 mm.

[0128] It should be noted that the positive electrode ribs can alternatively be placed in the exemplary cell so that they contact the negative electrode. Likewise, the negative electrode ribs can alternatively be placed in the exemplary cell so that they contact the positive electrode.

[0129] 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) having a 162 mm x 162 mm (262 cm 2 ). As shown, an exemplary separator of the present invention has 43 toothed ribs that are evenly spaced across the width of the separator in the cross-machine direction. The teeth of the positive electrode ribs on the separator of the present invention are aligned with 262 cm on the positive electrode. 2 The details of the control separators are further detailed in Table 4. It should be understood that the control separators #1, #2 and #3 are typical of current commercially available separators, currently commonly used in flooded lead acid batteries and currently available on the market.

[0130] Table 4

[0131] Partition Ribs [number (configuration)] Contact area (% of total area) Invented partition 43 (toothed ribs) 3.8％ Comparison #1 22(Solid rib) 4.8％ Comparison #2 18(Solid rib) 3.9％ Comparison #3 11(Solid rib) 2.9％

[0132] As stated, the inventors have found that maximizing the number of contact points while minimizing the contact area achieves the goal of increasing separator elasticity while keeping resistance under control. In addition, the toothed design helps promote acid mixing by taking advantage of any movement that the battery may experience. The teeth of the separator ribs can be separated from the nearest adjacent teeth by about 2.5mm to about 6.0mm. The inventors have found that a preferred non-restrictive distance is about 4.2mm between adjacent teeth. In addition, the teeth offset from adjacent rows are completely different to help promote acid mixing. The inventors have also found that the bottom portion helps to harden the back web enough to provide elasticity for NAM expansion.

[0133] It is to be understood that while the exemplary inventive ribs are shown and described as positive ribs, they may be disposed on the negative side of a separator, and that the negative ribs shown and described may be disposed on the positive side of a separator.

[0134] The positive electrode ribs or negative electrode ribs can also be any form or combination of the following: solid ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angular ribs, linear ribs, longitudinal ribs extending substantially along the machine direction of the porous membrane, side ribs extending substantially along the cross-machine direction of the porous membrane, transverse ribs extending substantially along the cross-machine direction of the separator, discrete teeth, toothed ribs, serrations, serrated ribs, stacked protrusions, stacked ribs, arcuate ribs, sinusoidal ribs, arranged in a continuous zigzag-like triangular wave-like manner, arranged in an intermittent discontinuous zigzag-like triangular wave-like manner, grooves, grooves, textured areas, embossing, depressions, pillars, mini pillars, porous, non-porous, mini ribs, cross-cut mini ribs and combinations thereof.

[0135] The positive or negative ribs may also be any form or combination of ribs defined by an angle that is neither parallel nor perpendicular to the edge of the separator. Furthermore, the angle may vary across the teeth or rows of ribs. An angled rib pattern may be preferred. RipTide TM Acid mixing rib shape, which can help reduce or eliminate acid stratification in certain batteries. In addition, the angle can be defined relative to the machine direction of the porous membrane, and the angle can be between about greater than zero degrees (0°) and about less than one hundred and eighty degrees (180°), and between about greater than one hundred and eighty degrees (180°) and about less than three hundred and sixty degrees (360°).

[0136] The ribs may extend uniformly from side edge to side edge across the width of the partition. This is referred to as a universal profile. Alternatively, the partition may have side panels adjacent to the side edges in which smaller ribs are disposed. These smaller ribs may be spaced closer together and smaller than the major ribs. For example, the smaller ribs may be 25% to 50% of the height of the major ribs. The side panels may also be flat. The side panels may help seal one edge of the partition to another edge of the partition, as is done when encapsulating the partition, as will be discussed below.

[0137] In selected exemplary embodiments, the height of at least a portion of the negative electrode ribs may preferably be about 5% to about 100% of the height of the positive electrode ribs. In certain exemplary embodiments, the height of the negative electrode ribs may be about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95% or 100% of the height of the positive electrode ribs. In other exemplary embodiments, the height of the negative electrode ribs may be no greater than about 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10% or 5% of the height of the positive electrode ribs.

[0138] In some selected embodiments, at least a portion of the porous membrane may have negative electrode ribs that are longitudinal or transverse or cross-cut ribs. The negative electrode ribs may be parallel to the top edge of the separator, or may be arranged at an angle thereto. For example, the negative electrode ribs may be oriented to about 0 °, 5 °, 15 °, 25 °, 30 °, 45 °, 60 °, 70 °, 80 ° or 90 ° relative to the top edge. The cross-cut ribs may be oriented to 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 ° relative to the top edge.

[0139] Specific exemplary embodiments may have a bottom portion. If present, it may have an average bottom height of about 5 μm to about 200 μm. For example, the average bottom height may be greater than or equal to about 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, or 200 μm. In addition, if present, its average bottom width may be about 0.0 μm to about 50 μm wider than the width of the teeth. For example, the average bottom width may be greater than or equal to about 0.0 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm wider than the width of the teeth.

[0140] Certain exemplary embodiments may have teeth or toothed ribs. If present, their average tip length may be from about 50 μm to about 1.0 mm. For example, the average tip length may be greater than or equal to about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 800 μm, 900 μm, 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1500 μm, 1600 μm, 1700 μm, 1800 μm, 1900 μm, 2000 μm, 2100 μm, 2200 μm, 2300 μm, 2400 μm, 2500 μm, 2600 μm, 2700 μm, 2800

[0141] 600μm, 700μm, 800μm, 900μm or 1.0mm. Alternatively, they may be not greater than or equal to 1.0mm, 900μm, 800μm, 700μm, 600μm, 500μm, 400μm, 300μm, 200μm, 100μm or 50μm.

[0142] At least a portion of the teeth or ribs of the toothed belt have an average root length of about 50 μm to about 1.0 mm. For example, the average root 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 not greater than or equal to about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0143] The average height of at least a portion of the teeth or toothed ribs (the sum of the bottom height and the height of the teeth) is about 50 μm to about 1.0 mm. For example, the average height can 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 can be not greater than or equal to about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm or 50 μm.

[0144] At least a portion of the teeth or toothed ribs may have an average center spacing within a row in the machine direction of from about 100 μm to about 50 mm. For example, the average center spacing may be greater than or equal to 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, and in similar increments up to 50 mm. Alternatively, they may not be greater than or equal to 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, and in similar increments up to 50 mm. In addition, adjacent rows of teeth or toothed ribs may be identically disposed at the same position in the machine direction or offset. In an offset configuration, adjacent teeth or toothed ribs are disposed at different positions in the machine direction.

[0145] The average height to base width ratio of at least a portion of the teeth or toothed ribs may be about 0.1:1.0 to about 500:1.0. For example, the average height to base width ratio may be about 0.1:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1,

[0146] Alternatively, the ratio of the average height to the bottom width may be not greater than or equal to about 500:1.0, 450:1.0, 400:1.0,

[0147] 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.

[0148] At least a portion of the teeth or toothed ribs may have an average base width to tip width ratio of about 1,000:1.0 to about 0.1:1.0. For example, the average base width to tip width ratio may 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. : 1.0, 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 may be no greater than about 1,000: 1.0, 950: 1.0, 900: 1.0, 850: 1.0, 800: 1.0, 750: 1.0, 700: 1.0, 650: 1.0, 600: 1.0, 550: 1.0, 500: 1.0, 450: 1.0, 400: 1.0, 350: 1.0, 300: 1.0, 250: 1.0, 200: 1.0,

[0149] 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.

[0150] It is to be understood that any rib pattern described herein may have spacing between columns to allow gas to rise during an overcharge event. In addition, an intermittent rib pattern may have no spacing in the machine direction between rows of intermittent ribs, which may provide strength if the partition is folded to form a package. In addition, the intermittent rib partition may be further embossed. It is also to be understood that any rib pattern or other protrusion may be disposed on any interior surface of the battery case or on any surface of either or both of the positive and negative electrodes. For batteries placed in a vehicle, a preferred embodiment may place the partition in a direction generally parallel to the direction of motion of the vehicle so as to take advantage of the start and stop motion of the vehicle.

[0151] It is believed that the improved separators described herein, such as the interrupted rib separators described herein, can further help prevent the formation of sulfate crystals and can also help provide more uniform heat distribution and / or heat mixing and / or heat or thermal dissipation across the separator (dissipating heat in a shorter time than known separators for flooded lead-acid batteries (e.g., solid rib separators). It is also believed that the exemplary interrupted rib separators described herein can also 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.

[0152] In various embodiments of the present disclosure, the disclosed separators provide reduced acid stratification, or even completely eliminate acid stratification, such that the mixing level or volume uniformity of the acid or electrolyte within a flooded lead-acid battery is 1.0 or nearly 1.0. In various embodiments, the separators disclosed herein are also low electrical impedance (ER) separators. In such embodiments, the separators may include improvements, such as improved fillers that increase the porosity, pore size, internal pore surface area, wettability, and / or surface area of ​​the separator. In certain embodiments, the improved fillers have a higher structural morphology and / or a reduced particle size and / or a different amount of silanol groups than previously known fillers, and / or are more hydroxylated than previously known fillers. The improved fillers can absorb more oil and / or can allow for the incorporation of larger amounts of processing oil during separator formation without simultaneously shrinking or compressing when the oil is removed after extrusion. For example, the improved separator may be formed using silica having an intrinsic oil absorption value of about 175-350 ml / 100 g, in certain embodiments, 200-350 ml / 100 g, in certain embodiments, 250-350 ml / 100 gm, and in certain further embodiments, 260-320 ml / 100 g, although other oil absorption values ​​are possible.

[0153] The filler can further reduce the so-called hydration spheres of the electrolyte ions, increasing their ability to traverse the membrane, thereby again reducing the overall resistance or ER of the cell (eg, enhanced flooded cell) or system.

[0154] The filler or fillers may contain species (e.g., magnetic species such as metals) that aid electrolyte and ion flow through the separator. This also results in a reduction in overall resistance when the separator is used in a flooded cell (e.g., an enhanced flooded cell).

[0155] The low ER microporous separators herein may further comprise new and improved pore morphologies and / or new and improved fibril morphologies, with the result that when such separators are used in such flooded lead-acid batteries, the separators contribute to significantly reducing the electrical resistance in flooded lead-acid batteries. Such improved pore morphologies and / or fibril morphologies may produce separators whose pores and / or fibrils approach a shish-kebab (or shish kabob) type morphology. Another way to describe the new and improved pore shapes and structures is a textured fibril morphology, where nodes of silica or nodes of silica are present in a kebab-type configuration on polymer fibrils (fibrils are sometimes referred to as shish) within a battery separator. In addition, in specific embodiments, the silica structure and pore structure of the separator according to the present invention can be described as a skeleton structure or a vertebral structure or a spine structure, where the silica nodes on the kebab of the polymer (along the fibrils of the polymer) look like vertebrae or discs (kebabs) and are sometimes oriented substantially perpendicular to the slender central spine or fibril [extended chain-like polymer crystals that approximate a spine-like shape (shish)].

[0156] In some cases, improved batteries comprising improved separators having improved pore morphology and / or fibril morphology can exhibit a 20% lower, in some cases 25% lower, in some cases 30% lower resistance, and in some cases, even more than 30% lower resistance ("ER") drop (which may reduce the internal resistance of the battery), while such separators retain and maintain a balance of other key ideal mechanical properties of lead-acid battery separators. In addition, in certain embodiments, the separators described herein have new and / or improved pore shapes compared to known separators, allowing more electrolyte to flow through or fill the pores and / or voids. The ultra-high molecular weight polyethylene in the separator may include a polymer that is a shish-kebab configuration, comprising a plurality of extended chain crystals (shish configuration) and a plurality of folded chain crystals (kebab configuration), wherein the average repetition or period of the kebab configuration is 1 nm to 150 nm, preferably, 10 nm to 120 nm, and more preferably, 20 nm to 100 nm (at least on the portion on the rib side of the separator). In specific embodiments of these low ER embodiments of the separator of the present invention, the separator for lead-acid batteries described herein comprises a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica; wherein the filler is selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica; 29 The molecular ratio of OH to Si groups in the filler measured by Si-NMR is in the range of 21:100 to 35:100, in certain embodiments, in the range of 23:100 to 31:100, in certain embodiments, 25:100 to 29:100, and in certain preferred embodiments, 27:100 or higher.

[0157] In certain selected embodiments, the disclosed separators exhibit reduced electrical resistance, for example, a resistance of no greater than about 200 mΩ·cm 2 、180mΩ·cm 2 、160mΩ·cm 2 , 140mΩ·cm 2 ,、120mΩ·cm 2 , 100mΩ·cm 2 、80mΩ·cm 2 、60mΩ·cm 2 , 50mΩ·cm 2 、40mΩ·cm 2 、30mΩ·cm 2 , or 20mΩ·cm 2 In various embodiments, the separators described herein exhibit about 20% or more reduction in ER compared to known separators of the same thickness. For example, a known separator may have 60 mΩ·cm 2 ER value; therefore, the separator of the same thickness according to the present invention may have an ER value of less than about 48mΩ·cm2 The separators described herein having a low ER may have any or all of the features set forth in U.S. Provisional Patent Application No. 62 / 319,959, filed April 8, 2016, to Daramic, LLC, the entire contents of which are incorporated herein by reference.

[0158] According to at least selected embodiments, the present disclosure is directed to improved lead-acid batteries, such as flooded lead-acid batteries, improved systems including lead-acid batteries, and / or battery separators, improved battery separators, improved vehicles including such systems, methods of making or using, or combinations thereof. According to at least certain embodiments, the present disclosure is directed to improved flooded lead-acid batteries, improved battery separators for such batteries, and / or methods of making, testing, or using such improved flooded lead-acid batteries, or combinations thereof. In addition, a method, system, battery, and / or battery separator for reducing acid stratification in a flooded lead-acid battery and improving cell life and performance is disclosed herein.

[0159] Preferred features of the exemplary separators disclosed herein may be having or providing improved conductance over a long period of time. Conductance may be determined, for example, by cold cranking current (CCA) measured in a Midtronics tester. For example, the CCA value of a lead-acid battery equipped with a separator of the present invention may show a 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% as measured by a Midtronics CCA tester over 30 days.

[0160] The porous membrane can be provided in various ways with a kind of additive, surfactant, reagent, filler or multiple additives.For example, the porous membrane can be coated with a kind of additive or multiple additives when the porous membrane is completed (for example, after extraction), and / or a kind of additive or multiple additives are added in the mixture for making the membrane.According to a preferred embodiment, the solution of additive or additive is applied to the surface of the porous membrane.This variant is particularly suitable for applying thermally unstable additives and additives that can be dissolved in the solvent used for subsequent extraction process.Particularly suitable as the solvent of the additive according to the present invention is low molecular weight alcohol, such as methanol and ethanol, and a mixture of these alcohols and water.Coating can occur on the side facing the negative electrode, on the side facing the positive electrode or on the two sides of the microporous membrane.

[0161] Preferred features of the exemplary separators disclosed herein may be having or providing improved conductance over a long period of time. Conductance may be determined, for example, by cold cranking current (CCA) measured in a Midtronics tester. For example, the CCA value of a lead-acid battery equipped with a separator of the present invention may show a 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% as measured by a Midtronics CCA tester over 30 days.

[0162] The porous membrane can be provided in various ways with a kind of additive, surfactant, reagent, filler or multiple additives.For example, the porous membrane can be coated with a kind of additive or multiple additives when the porous membrane is completed (for example, after extraction), and / or a kind of additive or multiple additives are added in the mixture for making the membrane.According to a preferred embodiment, the solution of additive or additive is applied to the surface of the porous membrane.This variant is particularly suitable for applying thermally unstable additives and additives that can be dissolved in the solvent used for subsequent extraction process.Particularly suitable as the solvent of the additive according to the present invention is low molecular weight alcohol, such as methanol and ethanol, and a mixture of these alcohols and water.Coating can occur on the side facing the negative electrode, on the side facing the positive electrode or on the two sides of the microporous membrane.

[0163] The coating can also be carried out by immersing the microporous membrane in the additive or the additive solution and then optionally removing the solvent (for example by drying). In this way, the coating of the additive can be combined with the extraction that is often carried out, for example, in the production of separators.

[0164] Another preferred option is to mix one or more additives into a mixture of thermoplastic polymer and optional fillers and other additives used to prepare the porous membrane. The homogeneous mixture containing the additives is then formed into a web material.

[0165] The separator of the present invention can be a low ER separator, a low water loss separator, and / or can have at least a portion including protrusions, intermittent ribs, serrated ribs, discontinuous ribs and / or the like (rather than solid ribs) to improve the acid mixing or conductivity of the separator. The protrusions include features such as short rib segments, small blocks, embossing, etc. The protrusions may be located on either or both sides of the separator. Typically, the protrusions will be at least on the side facing the positive electrode plate (positive active material or PAM). The protrusions can be arranged in rows, with the protrusions in each row spaced apart from each other and from the protrusions in adjacent rows. In some cases, the protrusions may be located on the side of the separator facing the positive active material, the side of the separator facing the negative active material (or NAM), or on both sides of the separator.

[0166] The separator of the present invention can be provided in the form of a sheet or in the form of a sheet separator, a cover, a sleeve, a bag, a package, a hybrid package, a plate cover, a plate silver cover (e.g., a plate silver cover under a plate cover in a five-point battery system, for example, a system including a positive electrode plate, a fiber mat described herein as a silver cover, a plate cover, a box, and a separator around the plate cover and / or around an adjacent negative electrode plate), etc. In certain embodiments, a microporous membrane covered with at least one fiber layer on at least one side can be provided as a bag or package. When a fiber layer is present, it is preferred that the microporous membrane has a larger surface area than the fiber layer. Therefore, when the microporous membrane and the fiber layer are combined, the fiber layer does not completely cover the microporous layer. Preferably, at least two opposing edge regions of the membrane layer remain uncovered to provide edges for heat sealing, which facilitates the formation of a bag or package. The separator can be processed to form a hybrid package. A hybrid package can be formed by folding the separator sheet in half and bonding the edges of the separator sheet together to form a package before, during, or after forming one or more incisions or openings. The sides are bonded together using welding or mechanical sealing to form a seam that connects one side of the separator sheet to the other side of the separator sheet. For example, welding can be accomplished using heat or an ultrasonic process. This process produces a package shape having a bottom folded edge and two side edges.

[0167] The separator of packaged form disclosed herein can be a hybrid package, and has one or more incisions or openings along the folding or sealing fold of the package. 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 entire edge length. The length of the opening can be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5 or 1 / 10 to 1 / 5 of the entire edge length. Hybrid package can have 1-5, 1-4, 2-4, 2-3 or 2 openings, which can be evenly or unevenly arranged along the length of the bottom edge. Preferably, there is no opening in the corner of the package. Can cut out incisions after the separator is folded and sealed to form the package, or can form incisions before the porous membrane is shaped as the package.

[0168] The separators as disclosed herein may be characterized by improved conductance over long periods of time. Conductance may be determined, for example, by cold cranking current (CCA) measured in a Midtronics tester. For example, the CCA value of a lead-acid battery equipped with a separator of the present invention may exhibit a 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% as measured by a Midtronics CCA tester over 30 days. In contrast, the decrease in CCA observed for conventional batteries under similar conditions is typically much greater.

[0169] The separators provided herein allow for the production of batteries with reduced water loss and float current in the battery compared to batteries made from conventional separators. In some embodiments, the reduction in water loss may exceed 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. In some embodiments, the reduction in float current may exceed 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. Batteries prepared with the disclosed separators exhibit reduced internal resistance increases over the entire time period, and in some cases, do not exhibit an increase in internal resistance.

[0170] In addition to reducing water loss and allowing for longer battery life, the separators that may be preferred are also designed to provide other benefits. With regard to assembly, the separators have a negative electrode cross-cut rib design to maximize bending stiffness and ensure the highest manufacturing productivity. To prevent short circuits during high-speed assembly and during later use, the separators have superior puncture resistance and oxidation resistance compared to standard PE separators.

[0171] According to at least selected embodiments, the present disclosure or invention is directed to an improved battery separator, a low ER or high conductivity separator, an improved lead-acid battery (e.g., a flooded lead-acid battery), a high conductivity battery, and / or an improved vehicle containing such a battery, and / or a method of making or using such a separator or battery, and / or a combination thereof. According to at least certain embodiments, the present disclosure or invention is directed to an improved lead-acid battery that contains an improved separator and exhibits increased conductivity.

[0172] It is believed that the improved separators described herein, such as the interrupted rib separators described herein, can further help prevent the formation of sulfate crystals and can also help provide more uniform heat distribution and / or heat mixing and / or heat or heat dissipation (dissipation of heat in a shorter time than known separators for flooded lead-acid batteries (such as solid rib separators). It is also believed that the exemplary interrupted rib separators described herein can also provide improved or faster or more efficient filling of flooded lead-acid batteries, gel batteries and / or enhanced flooded batteries.

[0173] In various embodiments, the separators disclosed herein are also low electrical resistance ("ER") separators. In such embodiments, the separator may include improvements, such as improved fillers that increase the porosity, pore size, internal pore surface area, wettability, and / or surface area of ​​the separator. In certain embodiments, the improved filler has a high structural morphology and / or a reduced particle size and / or a different amount of silanol groups than previously known fillers, and / or is more hydroxylated than previously known fillers. The improved filler can absorb more oil and / or can allow for the incorporation of larger amounts of processing oil during separator formation without simultaneous shrinkage or compression when the oil is removed after extrusion. For example, the improved separator can be formed using silica having an inherent oil absorption value of about 175-350 ml / 100g, in certain embodiments, an oil absorption value of about 200-350 ml / 100g, in certain embodiments, 250-350 ml / 100g, and in certain other embodiments, 260-320 ml / 100g, although other oil absorption values ​​are also possible.

[0174] The separator comprises one or more performance enhancing additives. The performance enhancing additive can be a surfactant. Specific 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, such as two or more anionic surfactants, two or more nonionic surfactants, or at least one ionic surfactant and at least one nonionic surfactant. The use of these specific suitable surfactants in combination with the inventive separator described herein can result in even further improved separators that, when used in a lead-acid battery, reduce water loss, reduce antimony poisoning, improve cycling, reduce float current, reduce float potential, and / or the like. Suitable surfactants include surfactants such as the following: alkyl sulfates, alkyl aryl sulfonates, alkylphenol-alkylene oxide addition products, fatty acid salts, alkyl naphthalene sulfonates, one or more sulfosuccinates (e.g., anionic sulfosuccinates), dialkyl esters of sulfosuccinates, amino compounds (primary amines, secondary amines, tertiary amines or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxide / mono- and dialkyl phosphate salts. Additives may include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, silicone-based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphates, and sucrose esters of fatty acids.

[0175] Battery separators can be combined with one or more additives, reagents and / or fillers in various ways. For example, one or more additives can be applied to the separator when the separator is completed (for example, after extracting and / or introducing the rubber), and / or one or more additives can be added to the mixture used to extrude and ultimately produce the separator. According to a specific preferred embodiment, the additive or additive solution (for example, an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for applying thermally unstable additives and additives that can be dissolved in solvents used to extract process oils. Particularly suitable as solvents for additives according to the present invention are low molecular weight alcohols, such as methanol and ethanol, and mixtures of these alcohols with water. Coating can occur on the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides. Coating can also occur during the extraction of the pore former in a solvent bath. In certain embodiments, before or after the introduction of the rubber component, any of the above methods can be used to combine the additive with the microporous membrane. In certain selected embodiments, a portion of the performance enhancing additive, such as a surfactant coating or a performance enhancing additive (or both) added to the extruder prior to making the separator, may bind to the antimony in the battery system and may passivate it and / or form compounds with it and / or cause it to fall into the slurry space of the battery and / or prevent it from being deposited on the negative electrode.

[0176] In certain embodiments, the additive (e.g., nonionic surfactant, anionic surfactant, or mixture thereof) may be present in at least the following density or addition amount: 0.5 g / m 2 1.0g / m 2 , 1.5g / m 2 , 2.0g / m 2 , 2.5g / m 2 3.0g / m 2 3.5g / m 2 4.0g / m 2 4.5g / m 2 5.0g / m 2 5.5g / m 2 , 6.0g / m 2 , 6.5g / m 2 , 7.0g / m 2 , 7.5g / m 2 , 8.0g / m 2 5.5g / m 2 , 9.0g / m 2 , 9.5g / m 2 or 10.0g / m 2 , or even up to about 20.0 g / m 2 The additives may be present on the separator in the following density or addition amount: 0.5-15 g / m 2, 0.5-10g / m 2 1.0-10.0g / m 2 1.5-10.0g / m 2 2.0-10.0g / m 2 2.5-10.0g / m 2 3.0-10.0g / m 2 3.5-10.0g / m 2 4.0-10.0g / m 2 4.5-10.0g / m 2 5.0-10.0g / m 2 , 5.5-10.0g / m 2 , 6.0-10.0g / m 2 , 6.5-10.0g / m 2 , 7.0-10.0g / m 2 , 7.5-10.0g / m 2 4.g / m 2 , 5.0-g / m 2 , 5.0-12.0g / m 2 or 5.0-15.0g / m 2 between.

[0177] Coating can also be done by immersing the battery separator in the additive or in a solution of the additive (solvent bath addition) and, if necessary, by drying, the application of the additive can be combined with extraction, such as is often done in separator production. Other preferred methods are spraying the surface with the additive, dipping, rolling or curtain coating one or more additives onto the separator surface.

[0178] Another preferred option is to add one or more additives to the mixture of thermoplastic polymer and optional fillers and other agents or additives used to produce the film. The additive-containing mixture is then formed into a web material.

[0179] In certain embodiments described herein, reduced amounts of anionic or nonionic surfactants are added to the separators of the present invention. In these cases, desired characteristics may include reduced total organic carbon (TOC) and / or reduced volatile organic compounds (VOC) (due to the lower amount of surfactant), and desired separators according to such embodiments may be produced.

[0180] In a particular embodiment, the additive can be represented by a compound of formula (I)

[0181]

[0182] in:

[0183] .R is a non-aromatic hydrocarbon group having 10 to 4200, preferably 13 to 4200 carbon atoms (which may be interrupted by oxygen atoms);

[0184] . ; or Preferably H, where k = 1 or 2;

[0186] .M is an alkali metal or alkaline earth metal ion, H+ or NH4 + , where not all variables M can be H at the same time + ;

[0187] .n = 0 or 1;

[0188] .m=0 or an integer from 10 to 1400, and

[0189] .x=1 or 2.

[0190] The ratio of oxygen atoms to carbon atoms in the compounds according to formula (I) is in the range of 1:1.5 to 1:30, and m and n cannot both be 0. However, it is preferred that only one of the variables n and m is not zero.

[0191] Non-aromatic hydrocarbyl groups are those that do not contain aromatic groups or are themselves representative of a class. The hydrocarbyl group may be interrupted by oxygen atoms (ie, contain one or more ether groups).

[0192] R is preferably a straight-chain or branched aliphatic hydrocarbon radical which may be interrupted by oxygen atoms. Saturated, non-crosslinking hydrocarbon radicals are quite particularly preferred.

[0193] By using the compound of formula (I) to produce battery separators, they can be effectively protected from oxidative damage.

[0194] Battery separators comprising compounds according to formula (I) are preferred, wherein:

[0195] R is a hydrocarbon radical having 10 to 180, preferably 12 to 75 and very particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20 and very particularly preferably 1 to 8 oxygen atoms, particularly preferably a radical of the formula R 2 —[(OC2H4)p(OC3H6)q]—, wherein:

[0196] .R 2 is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 carbon atoms;

[0197] P is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4, and

[0198] .q is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4;

[0199] Compounds in which the sum of p and q is from 0 to 10, in particular from 0 to 4, are particularly preferred;

[0200] on = 1, and

[0201] om=0.

[0202] Formula R2—[(OC2H4)p(OC3H6) q ]—should be understood to also include compounds in which the order of the groups in the square brackets is different from that shown. For example, compounds in which the groups in the brackets consist of alternating (OC2H4) and (OC3H6) groups are suitable according to the invention.

[0203] Additives in which R2 is a straight-chain or branched alkyl radical having 10 to 20, preferably 14 to 18, carbon atoms have proven particularly advantageous. OC2H4 preferably represents OCH2CH2, and OC3H6 represents OCH(CH3)2 and / or OCH2CH2CH3.

[0204] As preferred additives, particular mention may be made of alcohols (p = q = 0, m = 0), primary alcohols being particularly preferred, 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) of primary alcohols being preferred. Fatty alcohol alkoxylates are obtainable, for example, by reacting the corresponding alcohols with ethylene oxide or propylene oxide.

[0205] Additives of the m=0 type (which are insoluble or only sparingly soluble in water) and sulfuric acid have proven to be particularly advantageous.

[0206] Also preferred are additives containing compounds according to formula (I) wherein:

[0207] R is an alkyl radical having 20 to 4200, preferably 50 to 750 and quite particularly preferably 80 to 225 carbon atoms;

[0208] M is an alkali metal or alkaline earth metal ion, H + or NH4 + , especially alkali metal ions such as Li + 、Na + and K + or H + , where not all variables M can be H at the same time + ;

[0209] n = 0;

[0210] m is an integer from 10 to 1400, and

[0211] x = 1 or 2.

[0212] As suitable additives, polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers may be mentioned in particular, the acid groups of which are at least partially (e.g. preferably 40%, particularly preferably 80%) neutralized. The percentage refers to the number of acid groups. Very particularly preferred is poly(meth)acrylic acid which is completely in the form of a salt. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn and ammonium (NR4, where R is a hydrogen or carbon functional group). Poly(meth)acrylic acid refers to 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, Mw particularly preferably 1,000 to 15,000 g / mol, quite particularly preferably 1,000 to 4,000 g / mol. The molecular weight of poly(meth)acrylic acid polymers and copolymers is determined by measuring the viscosity of the polymer in a 1% aqueous solution neutralized with sodium hydroxide solution (Fikentscher constant).

[0213] Likewise suitable are copolymers of (meth)acrylic acid, in particular copolymers which contain, besides (meth)acrylic acid, ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate as comonomers. Copolymers containing at least 40 wt.-%, preferably at least 80 wt.-% of (meth)acrylic acid monomers are preferred, the percentages being based on the acid form of the monomers or polymers.

[0214] Neutralization of polyacrylic acid polymers and copolymers with alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, especially sodium hydroxide, is particularly suitable. In addition, the coating and / or additives used to strengthen the separator may include, for example, metal alkoxides, where the metal may be Zn, Na or Al by way of example only (not limitation), and, by way of example only, sodium ethoxide.

[0215] In certain embodiments, the microporous polyolefin separator layer may include a coating on one or both sides of such layer. Such coating may include a surfactant or other material. In particular embodiments, the coating is bonded to the membrane before the rubber is added, the coating is bonded to the membrane after the rubber is added, or the coating is bonded to the membrane both before and after the rubber is added. In certain embodiments, the coating may include one or more materials such as described in U.S. Patent No. 9,876,209B, which is incorporated herein by reference. Such coating may, for example, reduce the overcharge voltage of the battery system, thereby extending the battery life, while reducing grid corrosion and preventing dry-out and / or water loss.

[0216] The improved separator can be used in various battery (particularly lead-acid battery) applications. The battery can be a flooded battery, which can be a tubular or flat plate battery. The battery can be used in power applications, such as a golf cart (sometimes called a golf cart) battery, or other deep cycle applications, such as a solar or wind power battery.

[0217] Batteries, particularly flooded lead-acid batteries, particularly deep cycle batteries, having the improved separator disclosed herein may be characterized by having a lower float current (in amperes) after charging a 12 volt battery (i.e., 2.4 volts per cell, and a 12 volt battery has six cells) at a float voltage of 14.4 volts for a given time (e.g., 21 days, and the test may be extended to 84 days, with measurements taken every 21 days).

[0218] In addition, the inventive battery separator disclosed and described herein enables improved deep cycle batteries using such separators to have more consistent and lower end of charge (EOC) currents. Maintaining a lower EOC current indicates that the improved batteries described herein exhibit Sb poisoning inhibition. For example, as new deep cycle lead acid batteries age, more Sb is present in the battery, which means that the EOC current may increase during the life of the battery, thereby increasing the water consumption of the battery and thus reducing the overall life cycle performance of the battery. The inventive separator described herein means that the EOC current remains more consistent throughout the cycle life of the battery, thereby showing a reduction in Sb poisoning.

[0219] The end-of-charge current may sometimes refer to the float current required to maintain a fixed voltage for a lead-acid battery during idle periods. In antimony-containing lead-acid batteries, a typical behavior is illustrated with conventional lead-acid battery separators: antimony poisoning occurs and is observed by measuring an increase in the end-of-charge current over the life cycle. Antimony-inhibited battery separators currently available on the market or currently available best technology reduce antimony poisoning to some extent. However, separators discovered in accordance with the present invention are able to meet or even exceed the currently available best technology. The separators disclosed herein provide minimum antimony inhibition levels that are equivalent to but generally better than the known best available technology, while also further reducing the end-of-charge current to below the best technology available today.

[0220] Briefly, improved flexible battery separators are described and claimed herein that include at least one performance enhancing additive and / or coating that, when used in a flooded lead-acid battery (e.g., a deep-cycle flooded lead-acid battery), produce a deep-cycle flooded lead-acid battery that is improved or even significantly improved in terms of: enhanced antimony rejection (as measured by end-of-charge (EOC) voltage and demonstrated by improved EOC voltage rejection) relative to batteries made using separators made entirely of rubber and relative to batteries made using separators that do not contain rubber and / or latex components. With respect to antimony rejection, antimony poisoning can occur from the beginning of operation of a lead-acid battery (e.g., a flooded lead-acid battery, such as a deep-cycle flooded lead-acid battery). However, during the life of the battery, more antimony is released from repeated operation of the battery, which means that antimony rejection becomes more critical later in the battery's life. The improved separators described herein address this problem, allowing them to reject antimony even as the end of the battery's life is approached (e.g., more than 50% of the battery's built-in or expected life).

[0221] In addition, the improved flexible battery separators described herein also provide deep cycle flooded lead acid batteries that exhibit reduced float current at a steady state potential relative to batteries manufactured using previously known separators; reduced voltage and / or energy required to restore the battery to a full charge for deep cycle operation relative to deep cycle batteries manufactured using previously known separators; improved voltage control overall relative to batteries manufactured using previously known separators; and / or reduced grid corrosion relative to batteries manufactured using previously known separators.

[0222] In addition, it has been found in experiments using the separator of the present invention that Sb poisoning of batteries using the same separator is reduced. Sb poisoning is manifested by a reduction in the overpotential for hydrogen release or an increase in the rate of hydrogen release from the electrochemical reduction of water. This overpotential can be measured by measuring the hydrogen release current at a constant potential, and as a result, such experiments show that the separator according to the present invention performs better than the known separator. It was also determined in similar experiments that for batteries containing the separator according to the present invention, a difference in the peak of the large anode (positive current) in the CV curve can be observed. This peak originates from the oxidation of Pb on the surface of the lead working electrode to PbSO4. For conventional, comparative separators, the position of the peak shows a positive shift of 40-60 mV, which can be attributed to the presence of surface Sb changing the chemical process of Pb conversion to PbSO4. For batteries containing the separator according to the present invention, a smaller peak position shift is observed, which is a manifestation of the inhibition of the presence of Sb on the lead surface. This phenomenon, together with the significant reduction in the rate of hydrogen release, shows that the separator according to the present invention reduces the deposition of Sb on the negative electrode (lead electrode).

[0223] Improved separators for lead-acid batteries are disclosed herein. The separator may include a porous membrane, rubber and / or latex, and at least one performance enhancing additive or surfactant.

[0224] According to at least selected embodiments, aspects or objects, disclosed or provided herein are new or improved separators, battery separators, enhanced flooded battery separators, batteries, galvanic cells and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, galvanic cells and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved battery separators for enhanced flooded batteries. In addition, disclosed herein are methods, systems and battery separators for improving battery life, reducing internal resistance, increasing cold cranking current and / or improving uniformity in at least enhanced flooded batteries. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries, wherein the separator has performance enhancing additives or coatings, improved fillers, reduced tortuosity, increased wettability, reduced oil content, reduced thickness, reduced resistance and / or increased porosity, and the use of such separators in batteries reduces water loss from the battery, reduces acid stratification of the battery, reduces voltage drop of the battery and / or improves CCA of the battery. According to at least certain embodiments, provided separators include or exhibit performance enhancing additives or coatings, increased porosity, increased void volume, amorphous silica, higher oil absorbency silica, higher silanol silica, resistance to antimony poisoning, electrolyte mixing, retention of active material on the electrode, and any combination thereof.

[0225] According to at least certain embodiments, the present disclosure or invention is directed to improved flooded lead-acid batteries, improved battery separators, liners, composite separators, laminated separators, positive electrode packaging, negative electrode packaging and / or the like for such batteries, and / or methods of making, testing or using such improved flooded lead-acid batteries, or combinations thereof.

[0226] According to at least certain embodiments, aspects and / or objectives, the present invention, application or disclosure may provide solutions, new products, improved products, new methods and / or improved methods, and / or may address difficulties, needs and / or problems with PAM shedding, NAM shedding, electrode deformation, active material shedding, active material loss and / or physical separation, electrode efficiency, battery performance, battery life and / or cycle life, and / or may provide new battery separators, new battery technologies and / or new battery methods and / or systems that address the challenges posed by current lead-acid batteries or battery systems, particularly new battery separators, new battery technologies and / or new battery methods and / or systems that are suitable for preventing or inhibiting active material shedding from electrodes in enhanced flooded lead-acid batteries or other batteries such as other flooded batteries, AGM batteries, PSoC batteries, ISS batteries, ESS batteries or the like.

[0227] In at least one possible preferred embodiment, the separator is provided with a fiber mat for holding the active material on the electrode of the lead-acid battery. In at least one possible particularly preferred embodiment, the PE film separator is provided with at least one fiber mat for holding the active material on the electrode of the lead-acid battery. New or improved gaskets, separators, batteries, methods and / or systems are also disclosed, shown, claimed and / or provided. For example, according to at least certain embodiments, aspects and / or objectives, the present invention, application or disclosure may provide solutions, new products, improved products, new methods and / or improved methods, and / or may address difficulties, needs and / or problems with PAM shedding, NAM shedding, electrode deformation, active material shedding, active material loss and / or physical separation, electrode efficiency, battery performance, battery life and / or cycle life, and / or may provide new battery separators, new battery technologies and / or new battery methods and / or systems that address the challenges posed by current lead-acid batteries or battery systems, particularly new battery separators, new battery technologies and / or new battery methods and / or systems that are preferably suitable for preventing or inhibiting active material shedding from electrodes in enhanced flooded lead-acid batteries, PSoC batteries, ISS batteries, ESS batteries or the like.

[0228] In at least one embodiment, the separator is provided with a fiber mat for holding active materials on the electrodes of a lead-acid battery. And new or improved liners, separators, batteries, methods and / or systems are also disclosed, shown, claimed and / or provided. For example, in at least one possible preferred embodiment, the composite separator is provided with a fiber mat for holding active materials on the electrodes of a lead-acid battery. In at least one possible particularly preferred embodiment, the PE film separator is provided with at least one fiber mat for holding active materials on the electrodes of a lead-acid battery. According to at least certain embodiments, aspects and / or objectives, the present invention, application or disclosure may provide solutions, new products, improved products, new methods and / or improved methods, and / or may address difficulties, needs and / or problems with PAM shedding, NAM shedding, electrode deformation, active material shedding, active material loss and / or physical separation, electrode efficiency, battery performance, battery life and / or cycle life, and / or may provide new battery separators, new battery technologies and / or new battery methods and / or systems that address the challenges posed by current lead-acid batteries or battery systems, especially new battery separators, new battery technologies and / or new battery methods and / or systems that are preferably or particularly suitable for preventing or inhibiting active material shedding from electrodes in flooded lead-acid batteries, enhanced flooded lead-acid batteries, PSoC batteries, ISS batteries, ESS batteries or the like.

[0229] According to at least selected embodiments, aspects, or purposes, the present disclosure or invention is directed to or may provide new or improved separators, battery separators, enhanced flooded battery separators, fiber mats, batteries, galvanic cells, and / or methods of making and / or using such separators, battery separators, fiber mats, enhanced flooded battery separators, galvanic cells, and / or batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead acid battery separators for starter lighting ignition ("SLI") batteries, fiber mats, flooded batteries for deep cycle applications, and / or enhanced flooded batteries and / or systems, vehicles, and / or the like, which contain such separators, mats, or batteries, and / or improved methods of making and / or using such improved separators, mats, galvanic cells, batteries, systems, vehicles, and / or the like. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries and / or improved methods of making and / or using batteries having such improved separators. According to at least selected embodiments, the disclosure or invention is directed to separators, particularly separators for enhanced flooded batteries, having reduced resistance and / or increased cold cranking current. Additionally, methods, systems, and battery separators for improving battery life, reducing water loss, reducing internal resistance, increasing wettability, reducing acid stratification, improving acid diffusion, improving cold cranking current, and / or improving uniformity in at least enhanced flooded batteries are disclosed herein. According to at least particular embodiments, the disclosure or invention is directed to improved separators for enhanced flooded batteries, wherein the separator comprises one or more performance enhancing additives or coatings, increased porosity, increased void volume, amorphous silica, more oil absorbing silica, more silanol-rich silica, retention and / or improved retention of active materials on electrodes, and / or any combination thereof.

[0230] The compositions and methods of the appended claims are not limited to the scope of the specific compositions and methods described herein, which are intended to illustrate certain aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. In addition to the compositions and methods shown and described herein, variations of various compositions and methods are also intended to fall within the scope of the appended claims. In addition, although only specific representative compositions and method steps disclosed herein are specifically described, combinations of other compositions and method steps are also intended to fall within the scope of the appended claims, even if not explicitly listed. Therefore, combinations of steps, elements, components, or ingredients may be explicitly or less explicitly mentioned herein, but even if not explicitly stated, combinations of other steps, elements, components, or ingredients are also included herein.

[0231] Without departing from the spirit and essential attributes of the present invention, the present invention may be implemented in other forms, and therefore, when indicating the scope of the present invention, reference should be made to the appended claims rather than the foregoing description. Disclosed are components that can be used to implement the disclosed methods and systems. These components and other components are disclosed herein, and it should be understood that for all methods and systems, when disclosing combinations, subsets, interactions, groups, etc. of these components, although specific reference to each of their different individual and collective combinations and permutations may not be explicitly disclosed, each is specifically considered and described herein. This applies to all aspects of the present application, including but not limited to the steps in the disclosed methods. Therefore, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed using any specific embodiment or combination of embodiments of the disclosed methods.

[0232] The foregoing written description of the structure and method is given for illustrative purposes only. The embodiments are used to disclose exemplary implementations, including the best mode, and to enable those skilled in the art to implement the invention, including making and using any device or system and performing any combined method. These embodiments are not intended to be exhaustive or limit the invention to the precise steps and / or forms disclosed, and there may be many modifications and changes based on the teachings of the foregoing. The features described herein may be combined in any combination. The steps of the method described herein may be performed in any order that is physically possible. The patentable scope of the present invention is defined by the appended claims and may include other embodiments that occur to those skilled in the art. If these other embodiments have structural elements that are no different from the literal language of the claims, or if they include equivalent structural elements that are no substantially different from the literal language of the claims, these other embodiments are intended to be within the scope of the claims.

[0233] The compositions and methods of the appended claims are not limited to the scope of the specific compositions and methods described herein, which are intended to illustrate certain aspects of the claims. Any compositions and methods that are functionally equivalent fall within the scope of the claims. In addition to those shown and described herein, various changes in the compositions and methods also fall within the scope of the appended claims. In addition, although only certain representative compositions and method steps are disclosed and specifically described herein, combinations of other compositions and method steps are also intended to fall within the scope of the attached claims, even if not specifically described. Therefore, combinations of steps, elements, components, or ingredients may be explicitly or less explicitly mentioned herein, but combinations of other steps, elements, components, or ingredients are also included even if not explicitly stated.

[0234] When used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly indicates 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 a particular value and / or to another particular value. Similarly, when a numerical value is expressed as an approximation by using the antecedent "about", it should be understood that the particular value forms another embodiment. It should be further understood that the endpoints of each range are significant relative to the other endpoint and are independent of the other endpoint. "Optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes situations where the event or situation occurs and situations where the event or situation does not occur.

[0235] Throughout the specification and claims of this specification, the word "comprising" and variations of the word, such as "comprising in the participle form" and "comprising in the third person singular form", mean "including but not limited to", and are not intended to exclude, for example, other additives, components, integers or steps. The terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, and they are also disclosed. "Exemplary" or "for example" means "an example" and is not intended to convey the meaning that it is a preferred or ideal embodiment. Similarly, "such as" is not used in a restrictive sense, but for illustrative or exemplary purposes. Unlike in the examples, or where otherwise specified, all numbers used in the specification and claims to represent the quantity of ingredients, reaction conditions, etc. are not intended to limit the application of the doctrine of equivalents to the scope of the claims, and should at least be understood as being interpreted according to significant figures and conventional rounding methods.

[0236] Unless otherwise noted, all numbers indicating geometric shapes, dimensions, and so forth, used in the specification and claims are not intended to limit the application of the doctrine of equivalents to the scope of the claims and should at least be construed in light of significant digits and ordinary rounding techniques.

[0237] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs.Publications cited herein and the materials they cite are expressly incorporated herein by reference.

[0238] Furthermore, the invention illustratively disclosed herein suitably may be practiced in the absence of any element not specifically disclosed herein.

Claims

1. An assembly of a lead-acid battery separator and a fiber mat for a PSoC battery for an ISS vehicle, wherein: The overcharge-sensitive, electrolyte-absorbing fiber mat is changed from being part of the electrode assembly to becoming a unit with the separator; The fiber mat comprises bundled fibers, and the synthetic fiber diameter of the fiber mat is 7.2±0.5 μm; The average pore size of the fiber mat is smaller than the average particle size of the active material; The fiber mat has soluble fibers, a wetting agent and / or a gelling agent.

2. An assembly of a lead-acid battery separator and a fiber mat for a PSoC battery for an ISS vehicle, wherein: The overcharge-sensitive, electrolyte-absorbing fiber mat is changed from being part of the electrode assembly to becoming a unit with the separator; The separator is provided with an array of positive electrode ribs extending from the porous membrane in the machine direction and in contact with the fiber mat, and is provided with an array of negative electrode ribs extending from the porous membrane in the machine direction and in contact with the negative electrode to provide a spacing between the NAM and the backing mesh so that the NAM expansion does not affect the porous membrane, thereby preventing acid starvation of the negative electrode and the positive electrode.

3. An assembly of a lead-acid battery separator and a fiber mat for a PSoC battery for an ISS vehicle, wherein: The overcharge-sensitive, electrolyte-absorbing fiber mat is changed from being part of the electrode assembly to becoming a unit with the separator; The separator has three regions, adjacent regions have different intermittent rib patterns, the regions vary along the cross-cutting process direction of the separator; the quality of the pattern in each region is relatively consistent; The distance between the center ribs of adjacent rows is -5 mm to +5 mm, where negative numbers indicate the degree of overlap of the rows.

4. A method of depositing rubber onto a membrane by injection and drying, wherein: injecting a slurry containing rubber and / or latex into the fiber mat so that it is contained in and / or on the fiber mat; and The fiber mat is positioned adjacent to a battery separator and subsequently dried to enhance the capillary properties and / or electrolyte wetting properties of the fiber mat.

5. A lead-acid battery separator assembly, comprising: a porous membrane and a nonwoven fiber mat; the fiber mat is disposed adjacent to the porous membrane; and the lead-acid battery separator assembly has at least one of the following features: In the machine direction, there are spaces between the columns of ribs, but there are no spaces between the rows of ribs; The average pore size of the fiber mat is smaller than the average particle size of the active material; The average fiber diameter of the fiber mat is smaller than the average fiber diameter of the prior art; At least one side of the separator layer is provided with a coating formed by drying a liquid slurry containing rubber and / or latex; The fiber mat is disposed on the separator, not on the electrodes.

6. A lead-acid battery separator assembly, the assembly comprising a separator layer and a nonwoven fiber mat, the fiber mat being disposed on the separator, wherein: The fiber mat also has a thickness of 50-100 g / m 2 Area weight; thickness of 100-900μm; synthetic fiber diameter of 6.7-7.7μm; The separator layer comprises polyethylene, particulate filler and residual oil; and The polyethylene comprises a polymer in a shish-kebab configuration, the configuration comprising a plurality of extended chain crystals and a plurality of folded chain crystals; The average repetition period of the folded chain crystals is between 1 and 100 nm; one or both sides of the separator layer are coated with a liquid slurry containing rubber and / or latex (optionally silica and water), and then dried and / or formed into a film of such material on the surface of the separator layer; The residual oil content accounts for 10% to 40% of the total weight of the separator layer; the fiber mat has a viscosity of 6-14 mΩ·cm 2 The electrical impedance range is 4-5 μm, the average pore size is 4-5 μm, and the flow rate is 1500-2500 l / m 2 s range of air permeability.

7. The lead-acid battery separator assembly according to claim 6, wherein: The separator layer and the fiber mat are laminated together; The fiber mat has a thickness between 200-450 μm; the fiber mat has a resistance of less than 11 mΩ·cm 2 The electrical impedance of The fiber mat has a g / m 2 The fiber mat has an area weight of 15-21wt% of the binder content; The fiber mat has a tensile strength of 200 N / 50 mm in the machine direction; the fiber mat has a tensile strength of 150 N / 50 mm in a direction perpendicular to the machine direction; and / or the fiber mat comprises synthetic fibers with a diameter of 7.2 μm.

8. The lead-acid battery separator assembly according to claim 6, wherein: The fibers of the fiber mat are selected from: glass fibers, synthetic fibers and combinations thereof; preferably, the synthetic fibers are selected from: polypropylene, polyethylene terephthalate, acrylic acid, other plastics, polymers, homopolymers, copolymers, and any combination thereof; and / or The fiber mat contains additives selected from rubber, silica, soluble fiber, gelling agent, surfactant and combinations thereof. Preferably, the additives are selected from: applied as a coating, saturated in the fiber mat, dispersed in the fiber mat, added during the manufacturing process of the porous membrane, and any combination thereof.

9. The lead-acid battery separator assembly according to claim 6, wherein: The separator layer and the fiber mat are leaf-shaped; The separator layer and the fiber mat are sleeve-shaped; or The separator layer and the fiber mat are an encapsulation, preferably, the encapsulation is a hybrid encapsulation.

10. The lead-acid battery separator assembly of claim 6, wherein: The polyethylene is ultra-high molecular weight polyethylene; The separator layer comprises a particulate filler in an amount of 40% or more by weight of the separator layer; and The extended chain crystal is a shish configuration; the folded chain crystal is a kebab configuration.

11. The lead-acid battery separator assembly of claim 10, wherein: The filler is selected from the group consisting of: silicon dioxide, precipitated silicon dioxide, fumed silicon dioxide, precipitated amorphous silicon dioxide and any combination thereof; 29 The molecular ratio of OH to Si groups in the filler measured by Si-NMR is in the range of 21:100 to 27:100 or higher; The microporous membrane has a porosity greater than 64%; The processing plasticizer is selected from the group consisting of: processing oil, paraffin-based mineral oil, mineral oil and any combination thereof; and / or The particulate filler is present in the polymer in a kebab configuration.

12. The lead-acid battery separator assembly of claim 6, wherein: The separator layer is selected from the group consisting of: polyolefin, polyethylene, polypropylene, rubber, polyvinyl chloride, phenolic resin, cellulose, synthetic wood pulp, glass fiber, synthetic fiber and combinations thereof; and / or The separator layer comprises one of the following groups: a filler, a surfactant and a combination thereof. Preferably, the surfactant is selected from the group consisting of a nonionic surfactant, an ionic surfactant and an anionic surfactant.

13. The lead-acid battery separator assembly of claim 6, wherein: The separator layer comprises one of the following: ribs, intermittent ribs, serrated ribs, stacked ribs, embossed ribs, negative electrode cross-cut ribs, and any combination thereof; The separator layer comprises a plurality of discontinuous ribs; the plurality of discontinuous ribs are defined by an angular orientation, preferably, the angular orientation is relative to the processing direction of the separator layer, and the angular orientation is selected from the following angles: between greater than 0° and less than 180°, and between greater than 180° and less than 360°; and / or The separator layer includes one or more groups of ribs among the plurality of intermittent ribs; a first group of ribs within the one or more groups of ribs have a first angular orientation; and a second group of ribs within the one or more groups of ribs have a second angular orientation.

14. The lead-acid battery separator assembly of claim 6, wherein: The separator layer comprises rubber, preferably, the rubber is selected from the group consisting of latex, methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, brominated butyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, silicone rubber, copolymer rubber and combinations thereof; Preferably, the copolymer rubber is selected from the group consisting of styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / polypropylene rubber (EPM and EPDM), ethylene / vinyl acetate rubber, and combinations thereof; Preferably, the rubber is cross-linked or uncross-linked; or Preferably, the rubber is coated on at least one surface of the separator layer, the rubber is impregnated into the separator layer, or the rubber is mixed with a polymer for forming the separator layer.

15. A lead-acid battery comprising the lead-acid battery separator assembly according to claim 6.

16. The lead-acid battery according to claim 15, wherein: The battery comprises an alternating series of positive and negative electrodes; the positive electrode comprises an active material; Preferably, the separator layer and the fiber mat are inserted between the positive electrode and the negative electrode, or the separator layer and the fiber mat are a package wrapping the positive electrode, preferably, the package is a hybrid package; Preferably, the separator layer and the fiber mat are laminated into one unit; and / or Preferably, the separator layer and the fiber mat are adjacent to each other, the fiber mat is placed between the separator layer and the positive electrode, the fiber mat presses the active material, the fiber mat is incorporated into the active material, or the fiber mat is incorporated into the adhesive paper.

17. The lead-acid battery of claim 15, wherein: The average pore size of the fiber mat is smaller than the average particle size of the active material.

18. The lead-acid battery of claim 15, wherein: The battery is selected from the group consisting of a tubular battery, a planar battery, a golf cart battery, an inverter battery, an SLI battery, a flooded lead acid battery, a deep cycle battery, and a battery operating at a partial state of charge.

19. A vehicle comprising the lead-acid battery of claim 15.

20. The vehicle of claim 19, 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); and / or The vehicle undergoes a motion characterized by stop-start.

21. The lead-acid battery separator assembly of claim 6, wherein: The fiber mat has a thickness of 0.3 mm; the fiber mat has a thickness of 0.2 mm; the fiber mat has a thickness of 0.4 mm; or the fiber mat has a thickness of 0.1 to 0.5 mm.

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