Lead-acid battery separator, lead-acid battery and system with lead-acid battery

Abstract

A lead acid battery separator includes a porous membrane having a back mesh; when the back mesh is arranged in the battery, the back mesh is provided with a positive electrode surface facing the positive electrode and a negative electrode surface facing the negative electrode; the positive electrode surface is provided with machining direction positive electrode ribs extending in the machining direction, and the negative electrode surface is provided with machining direction crossing negative electrode ribs crossing the machining direction; the positive electrode ribs extend from the positive electrode surface of the back mesh by 8 microns to 1 mm in the processing direction, and the negative electrode ribs extend from the negative electrode surface of the back mesh by 50 microns to 75 microns in the processing direction; the distance between the negative electrode ribs in the machining direction is more compact than the distance between the positive electrode ribs in the machining direction. According to the battery separator of the present invention, competitive physicochemical properties which cannot be simultaneously achieved in the prior art are simultaneously improved, and at the same time, the battery separator has a maximum basis weight of 130 g / m < 2 >, a maximum resistance of 40 m omega.cm < 2 >, and a minimum puncture resistance of 12.5 N.

Description

[0001] This application is a divisional application. The priority date of the original PCT application is March 22, 2017; the original international filing date is March 22, 2018; the original international application number is PCT / US2018 / 023728; the date of entry into the Chinese national phase is November 19, 2019, and the application number is 201880033054.4; the original invention title is "Improved Separators, Lead-Acid Batteries, and Related Methods and Systems".

[0002] Related Applications

[0003] This application claims the priority and benefits of International Application No. PCT / US2017 / 023637 filed on March 22, 2017. Technical Field

[0004] According to at least selected embodiments, the present disclosure or invention is directed to new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, methods, and / or vehicles using the same components as above and / or methods of manufacturing and / or using such separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, and / or vehicles using the same components as above. According to at least specific embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead acid battery separators for use in inverter batteries, flooded batteries (for deep cycle applications), vehicle batteries (such as automotive starting lighting ignition ("SLI") batteries), batteries for automotive idle start-stop ("ISS") applications (such as those used in hybrid electric vehicles), and / or enhanced flooded batteries ("EFB") and / or improved methods of manufacturing and / or using such improved separators, primary cells, batteries, systems, vehicles, and / or the like. According to at least specific embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries and / or improved methods of manufacturing, testing, and / or using batteries having such improved separators. According to at least selected embodiments, the present disclosure or invention is directed to separators, particularly separators for enhanced flooded batteries, that have reduced separator electrical impedance ("ER"), reduced separator thickness, increased separator puncture strength, enhanced separator cross-machine direction ("CMD") stiffness, improved separator antioxidant properties, reduced separator basis weight, increased separator wettability, or any combination thereof. Additionally, disclosed herein are methods, systems, and battery separators for extending battery life, reducing water consumption, increasing wettability, reducing internal resistance, and / or improving uniformity in at least enhanced flooded batteries. 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, reduced resistance, reduced thickness, increased puncture strength, enhanced CMD stiffness, improved antioxidant properties, reduced basis weight, or any combination thereof. Background Art

[0005] Enhanced flooded batteries (“EFBs” or “EFB”) and Absorbent Glass Mat (“AGM”) batteries have been developed to meet the growing demand for power sources used in a variety of applications. The EFB system has a structure similar to that of traditional flooded lead-acid batteries, where the positive and / or negative electrodes are surrounded by a microporous separator and immersed in a liquid electrolyte. On the other hand, the AGM system does not contain free liquid electrolyte. Instead, the electrolyte is absorbed into a fiberglass mat, which is then layered on top of the electrodes. Historically, the AGM system has had higher discharge power, better cycle life, and greater cold cranking current than flooded battery systems. However, the manufacturing cost of AGM batteries is significantly higher, and they are more sensitive to overcharging. Therefore, the EFB system remains an attractive option for power and energy storage solutions for mobile and stationary applications. Such power and energy storage applications are diverse, such as: flat plate batteries, tubular batteries, vehicle SLI and hybrid vehicle ISS applications, deep cycle applications, golf cart or golf car and electric rickshaw batteries, batteries operating in a partial state of charge (“PSOC”), inverter batteries, and storage batteries for renewable energy.

[0006] The EFB system typically includes one or more battery separators that separate one or more positive electrodes from one or more negative electrodes within a lead-acid battery cell. The battery separator can have two main functions. First, the battery separator should keep one or more positive electrodes physically separated from one or more negative electrodes to prevent current from passing directly between the electrodes (electrical short circuit). Second, the battery separator should allow an ion flow between the positive and negative electrodes with the smallest possible ER. The battery separator can be made of a variety of different materials, but a battery separator made of a porous non-conductor has well met these two opposing functions. With this structure, the pores help the diffusion of ions between the electrodes, while the non-conductive polymer network prevents electrical short circuits.

[0007] In addition, other characteristics of the battery separator are desirable in addition to those listed above. For example, in addition to reduced resistance (ER), it may also be desirable for the separator to have increased puncture strength, enhanced transverse (CMD) stiffness, improved oxidation resistance, reduced separator thickness, and reduced basis weight.

[0008] A lower separator ER can improve battery performance and increase its charge acceptance (reduce recharge time and / or reduce charging current and / or voltage). If the puncture strength is too low, the separator may be punctured at the corners of the lead alloy electrodes during or at any time after assembly, which will result in a short circuit and premature battery failure. If the CMD stiffness is too low or too high, it may be difficult to handle the separator properly during battery assembly. Additionally, it may be desirable for the battery separator to have improved oxidation stability, which results in a longer battery cycle life. A lower basis weight can reduce manufacturing costs. Also, a reduced separator thickness may be desirable to reduce the overall size of the battery.

[0009] All of the above characteristics may lead to other desirable properties of lead-acid batteries, such as, for example, increased space for more electrolyte, reduced amount of lead in the electrodes, reduced battery size, and / or reduced time to charge the battery, to name just a few improvements.

[0010] Typical battery separators are microporous so that ions can pass between the positive and negative electrodes or plates. The separator can be made of polyolefins (such as polyethylene and polypropylene), wood, paper, natural or synthetic rubber, PVC, or fiberglass. In lead-acid storage batteries such as automotive batteries and / or industrial batteries and / or deep-cycle batteries, the battery separator is typically a microporous polyethylene separator; in some cases, such a separator may include a backing web and a plurality of ribs provided on one or both sides of the backing web. See: Handbook of Battery Materials, edited by Besenhard, J.O., Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), Chapter 9, pages 245-292. Some separators for automotive batteries are made in continuous lengths, rolled up, subsequently folded, and sealed along the edges (or a particular edge) to form a pouch or envelope or sleeve or bag for receiving the battery electrodes. For example, specific separators for industrial (or traction or deep-cycle storage) batteries are cut to approximately the same size (blocks or sheets) as the electrode plates.

[0011] For at least certain applications or batteries, there is still a need for improved separators to reduce ER, decrease separator thickness, increase separator puncture strength, enhance separator CMD stiffness, improve separator oxidation resistance, reduce separator basis weight, increase separator wettability, or any combination thereof. More particularly, there is still a need for improved separators and improved batteries incorporating the improved separators that can extend battery life, reduce battery failures, improve oxidative stability, increase charge termination ("EOC") current, reduce the current and / or voltage and / or time required to charge and / or fully charge the battery, minimize internal ER, increase puncture strength, enhance separator stiffness, decrease separator thickness, and / or reduce separator basis weight. Exemplary separator embodiments can be used in a variety of lead acid batteries, such as EFB, flooded batteries used in deep cycle battery applications, vehicles using such batteries, such as automotive SLI batteries, hybrid electric vehicle ISS batteries, and / or inverter batteries. Summary of the Invention

[0013] Details of one or more embodiments are set forth in the following description. Other features, objects, and advantages will be apparent from the specification and claims. According to at least selected embodiments, the present disclosure or invention can address the above problems or needs. According to at least certain purposes, aspects, or embodiments, the present disclosure or invention can provide or disclose new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, methods, and / or vehicles using the same components as above and / or methods of manufacturing and / or using such separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, and / or vehicles using the same components as above. According to at least certain embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead-acid battery separators for inverter batteries, flooded batteries for deep-cycle applications, vehicle batteries (such as automotive starting lighting ignition (“SLI”) batteries), batteries for automotive idle start-stop (“ISS”) applications (such as those used in hybrid electric vehicles), and / or enhanced flooded batteries (“EFB”) and / or improved methods of manufacturing and / or using such improved separators, primary 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 manufacturing, testing, and / or using such batteries with such improved separators. According to at least selected embodiments, the present disclosure or invention is directed to separators, particularly separators for enhanced flooded batteries, having reduced separator electrical resistance (“ER”), reduced separator thickness, increased separator puncture strength, enhanced separator cross-machine direction (“CMD”) stiffness, improved separator oxidation resistance, reduced separator basis weight, increased separator wettability, or any combination thereof. Additionally, disclosed herein are methods, systems, and battery separators for use in at least enhanced flooded batteries to extend battery life, reduce water consumption, increase wettability, reduce internal resistance, and / or improve uniformity. 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, reduced resistance, reduced thickness, increased puncture strength, enhanced CMD stiffness, improved oxidation resistance, reduced basis weight, or any combination thereof.

[0014] According to at least selected embodiments, the present disclosure or invention is directed to or can provide improved separators and / or batteries that overcome the above problems. For example, methods, systems, and improved battery separators that provide reduced ER, reduced separator thickness, increased separator puncture strength, enhanced separator CMD stiffness, improved separator oxidation resistance, reduced separator basis weight, or any combination thereof.

[0015] In selected embodiments of the present invention, the lead-acid battery separator can have about 130 g / m 2a basis weight of less than or equal to about 25 mN and a transverse bending stiffness greater than or equal to about 25 mN.

[0016] In certain other selected embodiments of the present invention, the lead acid battery separator may have a transverse stiffness of less than or equal to about 25 mN and a back web thickness of less than or equal to about 125 μm.

[0017] In some aspects of the present invention, the separator may have an impedance of less than or equal to about 40 mΩ·cm 2 an average puncture resistance greater than or equal to about 11.0 N, an antioxidant resistance greater than or equal to about 200% at 20 hours, an antioxidant resistance greater than or equal to about 100% at 40 hours, a back web thickness of less than or equal to about 125 μm, a residual oil content of less than or equal to about 20%, and a porous membrane having a residual oil content of greater than or equal to about 10%.

[0018] In other aspects of the present invention, the lead acid battery separator may have at least one set of ribs, where the at least one set of ribs is at least one of the following: solid ribs, discontinuous ribs, discrete discontinuous ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the transverse direction of the porous membrane, cross-cut ribs extending substantially in the transverse direction of the porous membrane, cross ribs extending substantially in the transverse direction of the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or discontinuous serrated manner, grooves, channels, textured areas, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0019] In a selected embodiment, the separator may have a first set of ribs extending from a first back web surface and having a first rib height measured from the first back web surface; a second set of ribs extending from a second back web surface and substantially orthogonal to the first set of ribs, and having a second rib height measured from the second back web surface, and a bottom web thickness of less than or equal to about 200 μm. The second set of ribs may have a height of less than or equal to about 75 μm and a back web thickness of less than or equal to about 100 μm.

[0020] An exemplary separator may have a total thickness between about 400 μm and about 2.0 mm.

[0021] In certain exemplary embodiments, a lead acid battery separator may have a first set of ribs that are at least one of the following: solid ribs, intermittent ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially along the processing direction of a porous or microporous membrane, transverse ribs extending substantially across the porous membrane, cross-cut ribs extending substantially across the porous membrane, cross ribs extending substantially across the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or intermittent serrated manner, grooves, channels, textured regions, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0022] In other selected embodiments, a lead acid battery separator may have a second set of ribs that are at least one of the following: solid ribs, intermittent ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially along the processing direction of a porous membrane, transverse ribs extending substantially across the porous membrane, cross-cut ribs extending substantially across the porous membrane, cross ribs extending substantially across the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or intermittent serrated manner, grooves, channels, textured regions, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0023] In selected embodiments, the present invention provides a lead acid battery substantially having a separator as described herein. The battery can be a flat plate battery, tubular battery, flooded lead acid battery, enhanced flooded lead acid battery, deep cycle battery, absorbed glass mat battery, tubular battery, inverter battery, vehicle battery, starting lighting ignition (“SLI”) battery, idle start-stop (“ISS”) battery, automotive battery, truck battery, motorcycle battery, all-terrain vehicle battery, forklift battery, golf cart battery, hybrid electric vehicle battery, electric vehicle battery, electric rickshaw battery, electric bicycle battery, or marine battery.

[0024] The battery can operate in a partially charged state, in motion or at rest, or in cycles of all of the above states.

[0025] In certain selected embodiments, the present invention provides a vehicle having a lead acid battery with a separator substantially as described herein. The vehicle can be an automobile, truck, motorcycle, all-terrain vehicle, forklift, golf cart, idle start-stop vehicle, hybrid electric vehicle, electric vehicle, electric rickshaw, electric bicycle, or marine vessel.

[0026] The battery can operate in a partially charged state, in motion or at rest, or in cycles of all of the above states.

[0027] In certain selected embodiments, the present invention provides a vehicle having a lead acid battery with a separator substantially as described herein. The vehicle can be an automobile, truck, motorcycle, all-terrain vehicle, forklift, golf cart, idle start-stop vehicle, hybrid electric vehicle, electric vehicle, electric rickshaw, electric bicycle, or marine vessel.

[0028] New or improved separators, battery separators, enhanced flooded battery separators, batteries, primary batteries, systems, methods, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, primary batteries, systems, and / or batteries; new or improved battery separators for enhanced flooded batteries; methods, systems, and battery separators having reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof; improved separators for enhanced flooded batteries, wherein the separator has reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, or any combination thereof; the provided separator comprises or exhibits reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof; the provided separator is used in battery applications for flat batteries, tubular batteries, vehicle SLI and HEV ISS applications, deep cycle applications, golf carts or golf ball carts, and electric rickshaw batteries, batteries operating in a partial state of charge (“PSOC”), inverter batteries, and storage batteries for renewable energy, and any combination thereof and / or analogs as shown, claimed, or described herein.

[0029] According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators, battery separators, enhanced flooded battery separators, batteries, primary batteries, systems, methods, and / or vehicles using the same components as described above, and / or methods of manufacturing and / or using such separators, battery separators, enhanced flooded battery separators, batteries, primary batteries, systems, and / or vehicles using the same components as described above. According to at least specific embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, vehicle batteries (such as automotive starting lighting ignition (“SLI”) batteries), batteries for automotive idle start-stop (“ISS”) applications (such as those used in hybrid electric vehicles), and / or enhanced flooded batteries (“EFB”), and / or improved methods of manufacturing and / or using such improved separators, primary batteries, batteries, systems, vehicles, etc. According to at least specific embodiments, the present disclosure or invention is directed to an improved separator for an enhanced flooded battery and / or an improved method of manufacturing, testing, and / or using such a battery with such an improved separator. According to at least selected embodiments, the present disclosure or invention is directed to a separator, particularly a separator for an enhanced flooded battery, having a reduced separator resistance (“ER”), a reduced separator thickness, an increased separator puncture strength, an enhanced separator cross-machine direction (“CMD”) stiffness, an improved separator oxidation resistance, a reduced separator basis weight, an increased separator wettability, or any combination thereof. Additionally, disclosed herein are methods, systems, and battery separators for use in at least enhanced flooded batteries to extend battery life, reduce water consumption, increase wettability, reduce internal resistance, and / or improve uniformity. 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, a reduced resistance, a reduced thickness, an increased puncture strength, an enhanced CMD stiffness, an improved oxidation resistance, a reduced basis weight, or any combination thereof.

[0030] According to at least selected embodiments, the present disclosure is directed to improved lead acid batteries (such as flooded lead acid batteries), including improved systems of lead acid batteries and / or battery separators, improved battery separators, improved vehicles (which include such systems), methods of manufacturing, testing, or using, or combinations thereof. According to at least specific embodiments, the present disclosure or invention is directed to improved flooded lead acid batteries, improved battery separators for such batteries, and / or methods of manufacturing, testing, or using such improved flooded lead acid batteries, or combinations thereof. Additionally, disclosed herein are methods, systems, batteries, and / or battery separators for reducing resistance, reducing separator thickness, increasing separator puncture strength, enhancing separator CMD stiffness, improving separator oxidation resistance, reducing separator basis weight, increasing separator wettability, or any combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Illustratively shows an exemplary flooded lead - acid battery.

[0032] Figure 2 Illustratively shows two exemplary surfaces of the separator of the present invention.

[0033] Figures 3A to 3C Depicts an embodiment of an exemplary separator and its various key dimensions. Figure 3A Illustratively depicts the positive electrode facing the surface of the exemplary separator. Figure 3B Is a cross - section of the exemplary separator shown along the processing direction (determined by A - A in Figure 3A ) in FIG. Figure 3C Is a cross - section of the exemplary separator shown along the transverse direction (determined by B - B in Figure 3B ) in FIG.

[0034] Figures 4A to 4C Depicts different embodiments of the separator with exemplary rib profiles.

[0035] Figure 5 Shows the tip for puncture - testing the separator.

[0036] Figure 6 Is a schematic diagram of the bending test of the separator.

[0037] Figure 7A Is a schematic diagram of the elongation - rate test sample.

[0038] Figure 7B Shows the sample clamp for elongation - rate testing. Detailed Description of the Invention

[0039] By referring to the following detailed description of the invention, examples, and figures (i.e., “FIGS”), the embodiments described herein can be more easily understood. Various batteries, vehicles or devices, and methods for preventing acid stratification, etc. are described herein. However, these are not limited to the specific embodiments presented in the detailed description of the invention, examples, and figures. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adjustments will be obvious to those skilled in the art without departing from the disclosed subject matter.

[0040] Lead - acid battery

[0041] See Figure 1, an exemplary flooded lead-acid battery 50, such as an EFB, is provided with an array 50a in which positive electrodes 52 and negative electrodes 54 alternate, which causes the positive electrodes 52 and negative electrodes 54 to be interleaved with each other. The array 50a is also provided with separators 100 interleaved between each pair of electrodes 52, 54, which causes the separators 100 to separate the electrodes 52, 54 to prevent contact between the electrodes 52, 54. The array 50a is fully immersed in a sulfuric acid (H2SO4) electrolyte 56 (e.g., sulfuric acid having an exemplary specific gravity between about 1.20 and about 1.35 relative to water). The positive electrode 52 is in electrical communication with a positive terminal 51, and the negative electrode 54 is in electrical communication with a negative terminal 53.

[0042] Now refer to Figure 2 , the separator 100 includes a porous membrane and may also be provided on either or both of its surfaces with one or more sets of ribs extending from the porous membrane 102. The porous membrane 102 has a surface 102p facing the positive electrode (since this surface will face the positive electrode when the separator is placed in a lead-acid battery) and a surface 102n facing the negative electrode (since this surface will face the negative electrode when placed in a lead-acid battery). Positive ribs 104 may extend from the surface 102p facing the positive electrode, and negative ribs 106 may extend from the surface 102n facing the negative electrode. The separator is further provided with a processing direction and a transverse direction as indicated by the arrows, with the md representing the processing direction and the cmd representing the transverse direction, and these two directions are generally orthogonal to each other. An exemplary separator may have positive ribs 104 extending substantially in the processing direction md and negative ribs 106 extending substantially in the transverse direction cmd. Return to refer to Figure 1 , the processing direction md of the exemplary separator 100 extends substantially between the top and bottom of the battery 50, and the transverse direction cmd is substantially orthogonal to the processing direction md.

[0043] In addition, the exemplary separator 100 may be coupled to, adjacent to, or laminated with one or more fiber mats (not shown).

[0044] There are not many restrictions on the lead-acid batteries described herein, and they can be flooded lead-acid batteries (such as enhanced flooded lead-acid batteries), absorbent glass mat ("AGM") batteries, valve-regulated lead-acid ("VRLA") batteries, gel batteries, and / or similar batteries. In some preferred embodiments, the lead-acid batteries described herein are flooded lead-acid batteries, at least because some of the disclosures herein are dedicated to solving problems of flooded lead-acid batteries, especially flooded lead-acid batteries operating in a partially charged state or being in a partially charged state, namely acid stratification and active material shedding.

[0045] As described herein, exemplary separators can be used in lead-acid batteries for various applications. These applications can include, for example: partial state of charge applications, deep cycle applications, automotive applications, truck applications, motorcycle applications, power applications (such as forklifts, golf carts (also known as golf cars), etc.), electric vehicle applications, hybrid electric vehicle ("HEV") applications, ISS vehicle applications, electric rickshaw applications, electric tricycle applications, electric bicycle applications, marine applications, energy harvesting and storage applications (such as the harvesting and storage of renewable and / or alternative energy, such as wind energy, solar energy, etc.). Additionally, exemplary separators can be used in various batteries. Such exemplary batteries can include, for example: flooded lead-acid batteries (such as enhanced flooded lead-acid batteries), AGM batteries, VRLA batteries, flat plate batteries, tubular batteries, partial state of charge batteries, deep cycle batteries, automotive batteries, truck batteries, motorcycle batteries, power batteries (such as forklift batteries, golf cart (also known as golf car) batteries, and similar batteries), electric vehicle batteries, hybrid electric vehicle ("HEVs") batteries, ISS vehicle batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, marine batteries, energy harvesting and storage batteries (such as the harvesting and storage of renewable and / or alternative energy, such as wind energy, solar energy, etc.).

[0046] Separator

[0047] Separator 100 must prevent electrical conductance between electrodes 52, 54 while allowing ionic conduction between electrodes 52, 54. Thus, an exemplary embodiment of separator 100 of the present invention preferably includes a porous membrane, such as a microporous membrane, mesoporous membrane, or macroporous membrane having pores less than about 5 μm, preferably less than about 1.0 μm, or pores greater than about 1.0 μm. In a particular preferred embodiment, the exemplary porous membrane is a microporous membrane having a pore diameter of about 0.1 μm and a porosity of about 60% to about 68%.

[0048] There are not many restrictions on the porous membrane, and it can be any porous membrane, having pores of any size (e.g., macropores, micropores, nanopores, etc.) and made of any material resistant to acidic electrolytes. In some preferred embodiments, the porous membrane is a microporous membrane such as a battery separator. For example, the microporous membrane can be any polyethylene battery separator manufactured by or any other lead-acid battery separator manufacturer, either currently or in the future.

[0049] In some embodiments, the pore diameter of the porous membrane is less than 5 μm, preferably less than 1 μm. Preferably, more than 50% of the pores are 0.5 μm or smaller. It may be preferred that at least 90% of the pores have a diameter less than 0.9 μm. The microporous separator preferably has an average pore diameter in the range of 0.05 μm - 0.9 μm (in some cases 0.1 μm - 0.3 μm).

[0050] Physical Description

[0051] Referring now to Figures 3A-3C , exemplary separator 100 has a top edge 101, a bottom edge 103, side edges 105a and 105b, a machine direction (“MD”), and a cross machine direction (“CMD”). Exemplary separator 100 may be provided with a backsheet 102 of a porous membrane, and a series of primary or positive ribs 104 extending from a surface 102p facing the positive electrode. As shown, ribs 104 are segmented or serrated. However, ribs 104 may be ribs, grooves, textured areas, serrated protrusions or serrated ribs, solid ribs, stack-like protrusions or stack-like ribs, discontinuous ribs, angled ribs, linear ribs or curved or sinusoidal ribs, serrated ribs, protrusions, depressions and / or the like extending into or from backsheet 102 or any combination thereof. The exemplary embodiment places separator 102 in the battery such that ribs 104 face the positive electrode (not shown), but this is not required. If ribs 104 face the positive electrode, they may be referred to as positive ribs. Figure 3B Separator 100 is shown along the machine direction md, with the backsheet thickness (thickness 背网 ), the positive rib height (height 正 ), and the negative rib height (height 负 ) shown, the combination of which equals the total separator thickness (thickness 总 ). Figure 3B The bottomsheet thickness thickness 底网 is further shown, which is the sum of the backsheet thickness thickness 背网 and the negative rib height height 负 . Figure 3C Separator 100 is shown along the cross machine direction, which shows negative ribs 106 (discussed below and further referred to as “negative cross ribs” or “NCR” or “NCRs”) being transversely disposed in the cross machine direction. Figure 3C The positive rib serrations 104s are further shown. Separator 100 will typically be placed in the battery such that the negative cross ribs face the negative electrode, but this is not required. In the absence of negative cross ribs, the backsheet thickness thickness 背网 equals the bottomsheet thickness thickness 底网 . It should be understood that Figures 3A to 3C is not drawn to scale.

[0052] Rib

[0053] In certain selected aspects of the present invention, one or both of the positive and negative ribs can be solid ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the transverse direction of the porous membrane, cross-cut ribs extending substantially in the transverse direction of the porous membrane, cross ribs extending substantially in the transverse direction of the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or intermittent serrated pattern, grooves, channels, textured areas, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs and / or the like and / or combinations thereof.

[0054] In various possible preferred embodiments, the porous membrane 102 can have ribs 104, 106 provided on either surface of the membrane 102, which can be positive ribs or negative cross ribs. The ribs 104, 106 can be ribs, grooves, textured areas, serrated protrusions or serrated ribs, solid ribs, stack-like protrusions or stack-like ribs, intermittent ribs, angled ribs, linear ribs or curved or sinusoidal ribs, serrated ribs, protrusions, depressions and / or analogs extending into or out of the back web or any combination thereof. In some embodiments, the ribs can exist in a pattern, such as they can be only on one surface of the porous membrane, or on both surfaces of the membrane. The separator can include positive ribs on the first side or surface, or the positive side or surface, or the front side or surface of the porous membrane, and negative cross ribs on the second side or negative side or back side of the separator. Such negative cross ribs can be smaller and closer spaced than the positive ribs. The positive rib 104 can have a height between 8 μm and 1 mm 正 , and can be spaced 1 μm to 20 mm apart, while the thickness of the back web of the preferred microporous polyolefin porous membrane (excluding ribs or protrusions) 背网 can be from about 50 μm to about 500 μm (e.g., in certain embodiments, less than or equal to about 125 μm). For example, the ribs can be separated by 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, and in similar increments up to 20 mm.

[0055] The negative cross ribs (NCRs) 106 can have a height between about 25 μm and about 100 μm 负 , and preferably between about 50 μm - 75 μm, but can be as small as 25 μm. In some cases, the NCRs 106 can be from about 25 μm to about 250 μm or preferably from about 50 μm to 125 μm or preferably from about 50 μm - 75 μm.

[0056] In some embodiments, the positive electrode rib 104 may be on the first surface of the porous membrane 102, and the negative electrode or negative electrode cross rib 106 may be on the second surface of the porous membrane and be substantially 90° relative to the positive electrode rib 104. In some embodiments, the positive electrode rib 104 may be on the first surface of the porous membrane 102 and is typically arranged orthogonally to the top edge 101 of the separator 100, while the negative electrode or negative electrode cross rib 106 may be on the second surface of the porous membrane 102 and is typically arranged parallel to the top edge 101 of the separator 100. In some embodiments, the positive electrode rib 104 may be on the first surface of the porous membrane and is typically arranged parallel to the processing direction md of the separator 100, while the negative electrode or negative electrode cross rib 106 may be on the second surface of the porous membrane 102 and is typically arranged parallel to the transverse direction cmd of the separator. In some embodiments, the positive electrode rib 104 may be on the first surface of the porous membrane and is arranged at an angular orientation relative to the processing direction md of the separator 100 between greater than about 0° and less than about 180° or greater than about 180° and less than about 360°; while the negative electrode or negative electrode cross rib 106 may be on the second surface of the porous membrane and is typically arranged parallel to the top edge 101 of the separator 100 or the transverse direction cmd. In some embodiments, the positive electrode rib 104 may be on the first surface of the porous membrane, while the negative electrode micro rib 106 may be on the second surface of the porous membrane 102 and is typically arranged parallel to the positive electrode rib 104 on the first surface of the porous membrane.

[0057] In certain preferred embodiments, the ribs may be serrated. The serrated protrusions 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.

[0058] The serrated protrusions or serrated ribs may have an average base length of 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.

[0059] If serrated protrusions or serrated ribs are present, they can have an average height of from about 0.05 mm to about 4 mm. For example, the average height 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. For embodiments in which the height of the serrated protrusions is the same as the rib height, the serrated ribs can also be referred to as protrusions. Such ranges can be applicable to separators for industrial traction start / stop batteries, where the total thickness of the separator can typically be from about 1 mm to about 4 mm, and automotive start / stop batteries, where the total thickness of the separator can be somewhat smaller (e.g., typically about 0.3 mm to about 1 mm).

[0060] The serrated protrusions or serrated ribs can have an average center-to-center spacing of from about 0.1 mm to about 50 mm within a row in the processing direction. For example, the average center-to-center spacing can 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. Additionally, adjacent rows of serrated protrusions or serrated ribs can be similarly positioned in the same location in the processing direction or offset. In an offset configuration, adjacent serrated protrusions or serrated ribs are positioned at different locations in the processing direction. Figure 3A Serrated ribs are shown in an offset configuration.

[0061] The serrated protrusions or serrated ribs can have an average height-to-bottom width ratio of from about 0.1:1 to about 500:1. For example, the average height-to-bottom width ratio can 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.

[0062] The serrated protrusions or serrated ribs may have an average ratio of bottom width to tip width of from about 1000:1 to about 0.1:1. For example, the average ratio of bottom width to tip width may be greater than or equal to about 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1, and / or less than or equal to 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.

[0063] In some embodiments, the separator may be characterized by a combination of ribs, serrated protrusions or serrated ribs, depressions, or combinations thereof. For example, the separator may have a series of serrated ribs extending from the top to the bottom of the separator, and a second series of serrated ribs extending horizontally across the separator. In other embodiments, the separator may have an alternating sequence of serrated ribs, depressions, continuous, discontinuous, or discontinuous solid ribs, or combinations thereof.

[0064] In some selected embodiments, the porous separator may have negative longitudinal or cross ribs as protrusions on opposite faces of the membrane. The negative ribs or back ribs may be parallel to the top edge of the separator, or may be set at an angle thereto. For example, relative to the top edge, the cross ribs may be oriented at about 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15°, or 5°. Relative to the top edge, the cross ribs may be oriented at about 90°-60°, 60°-30°, 60°-45°, 45°-30°, or 30°-0°. Generally, the cross ribs are located on the surface of the membrane facing the negative electrode. In some embodiments of the present invention, the ribbed membrane may have a cross-cut 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 负。In some embodiments of the present invention, the ribbed membrane may have a cross-cut rib height of not 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.

[0065] In some embodiments of the present invention, the ribbed membrane may have a cross-cut rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the present invention, the ribbed membrane may have a cross-cut rib width of not 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.

[0066] In certain selected embodiments, the porous membrane may have a cross-cut rib height of about 0.10 - 0.15 mm and a longitudinal rib height of about 0.10 - 0.15 mm. In some embodiments, the porous membrane may have a cross-cut rib height of about 0.10 - 0.125 mm and a longitudinal rib height of about 0.10 - 0.125 mm.

[0067] Thickness

[0068] In certain selected embodiments, the exemplary microporous membrane may have a backing web thickness of at least 50 μm, 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 Thickness 背网 。The ribbed separator may have a backing web thickness of not greater than 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, 0.1 mm, or 50 μm. In some embodiments, the microporous membrane may have a backing web thickness between about 0.050 - 1.0 mm, 0.050 - 0.8 mm, 0.050 - 0.5 mm, 0.050 - 0.4 mm, or 0.050 - 0.3 mm. In some embodiments, the microporous membrane may have a backing web thickness of about 125 μm or 200 μm.

[0069] In certain selected embodiments, the exemplary separator may have a total thickness that can be at least about 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, or greater and up to about 1.0 mm to about 2.0 mm or greater Total thickness 总 。

[0070] Basis weight

[0071] In certain embodiments, an exemplary separator may be characterized by a basis weight (also referred to as areal weight), which is measured in g / m 2 2. Exemplary separators may exhibit a reduced basis weight. For example, an exemplary separator may have a basis weight of less than or equal to 140 g / m 2 , less than or equal to 130 g / m 2 , less than or equal to 120 g / m 2 , less than or equal to 110 g / m 2 , less than or equal to 100 g / m 2 , less than or equal to 90 g / m 2 or lower. Exemplary separators preferably have a basis weight of from about 130 g / m 2 to about 90 g / m 2 or lower and more preferably from about 120 g / m 2 to about 90 g / m 2 or lower.

[0072] The basis weight is simply measured by weighing a sample and then dividing that value by the area of the sample. For example, take a sample that is 1.0 m by 1.0 m and weigh it. The area is calculated without considering any ribs, grooves, protrusions, etc. As an example, a 1.0 m by 1.0 m ribbed separator sample would have the same area as a 1.0 m by 1.0 m flat separator sample.

[0073] Envelope

[0074] Separator 100 may be provided as a flat plate, one or more sheets in a leaf-like, wrapped, sleeve-like, or as an envelope or bag-like separator. An exemplary envelope separator may encapsulate the positive electrode (“positive electrode encapsulating separator”), which causes the separator to have two inner sides facing the positive electrode and two outer sides facing the adjacent negative electrode. Alternatively, another exemplary envelope separator may encapsulate the negative electrode (“negative electrode encapsulating separator”), which causes the separator to have two inner sides facing the negative electrode and two outer sides facing the adjacent positive electrode. In such an envelope separator, the bottom edge 103 may be a folded or sealed seam edge. Further, the side edges 105a, 105b may be continuously or intermittently sealed seam edges. The edges may be bonded or sealed by adhesives, heat, ultrasonic welding, and / or similar methods or any combination thereof.

[0075] Some other exemplary embodiments of the separator assembly configuration include: multiple ribs 104 facing the positive electrode, multiple ribs 104 facing the negative electrode, a negative or positive envelope, a negative or positive sleeve, a negative or positive hybrid envelope, both electrodes may be encapsulated or sheathed, and any combination thereof. For example, FIGS. 4A-4C depict several embodiments of ribbed separators (such as sheets, sleeves, envelopes, or bags) with different rib patterns. It may be preferred that the ribs shown are positive ribs of a negative electrode plate envelope (negative electrode plate within the envelope).Figure 4A An angled rib pattern may be preferred RipTide TM An acid mixing rib pattern, which can help reduce or eliminate acid stratification in a particular battery. Figure 4B The pattern may be a longitudinal serrated rib pattern. Figure 4C The pattern may be a diagonally offset rib pattern. The negative surface may be ribless (smooth), have the same ribs, smaller ribs, longitudinal micro ribs, cross micro ribs or NCRs, diagonal ribs, or a combination thereof.

[0076] A particular exemplary separator may be processed into a hybrid envelope. The hybrid envelope may be provided by forming one or more slits or openings before, during, or after folding the separator sheet in half and bonding the edges of the separator sheet together to form an envelope. The length of the opening may be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the entire edge length. The length of the opening may be from 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the entire edge length. The hybrid envelope may have 1 - 5, 1 - 4, 2 - 4, 2 - 3, or 2 openings, which may be arranged uniformly or non - uniformly along the bottom edge length. Preferably, there are no openings at the envelope corners. The slit may be cut after the separator is folded and sealed to form an envelope, or the slit may be formed before shaping the porous membrane into an envelope.

[0077] In combination with a fiber mat

[0078] In certain embodiments, the exemplary porous membrane may be further laminated to another layer, such as a fiber mat having enhanced wicking properties and / or increased electrolyte wetting or retention. The fiber mat may be woven, non - woven, glass, or synthetic, single - layer, multi - layer (where each layer may have the same, similar, or different properties as the other layers), or any combination thereof.

[0079] When there is a fibrous layer, preferably, the microporous membrane has a larger surface area than the fibrous layer. Thus, when the microporous membrane and the fibrous layer are combined, the fibrous layer does not completely cover the microporous layer. Preferably, at least two opposite edge regions of the membrane layer remain uncovered to provide edges for heat sealing, which is advantageous for the optional formation of a bag or envelope. Such a fibrous mat can have a thickness of at least 100 μm, and in some embodiments, at least about 200 μm, at least about 250 μm, at least about 300 μm, at least about 400 μm, at least about 500 μm, at least about 600 μm, at least about 700 μm, at least about 800 μm, at least about 900 μm, at least about 1 mm, at least about 2 mm, and so on. The subsequent laminated separator can be cut into sheets. In a particular embodiment, the fibrous mat is laminated to the ribbed surface of the microporous membrane. In a particular embodiment, the improved separator described herein provides operational and / or assembly advantages to battery manufacturers because it can be supplied in roll form and / or sheet form. And as previously described, the improved separator can be a stand-alone separator sheet or layer without the addition of one or more fibrous mats or the like.

[0080] Composition

[0081] The porous membrane can be made from the following: natural or synthetic substrates, processing plasticizers and fillers, and optionally, other additives and / or coatings and / or the like.

[0082] Substrate

[0083] In a particular embodiment, exemplary natural or synthetic substrates can include: polymers, thermoplastic polymers, phenolic resins, natural or synthetic rubbers, synthetic wood pulp, glass fibers, synthetic fibers, cellulose fibers, and any combination thereof. In a particular preferred embodiment, the exemplary separator can be a microporous membrane made of a thermoplastic polymer. Exemplary thermoplastic polymers can in principle include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. In a particular preferred embodiment, exemplary thermoplastic polymers can include vinyl polymers and polyolefins. In a particular embodiment, vinyl polymers can include, for example, polyvinyl chloride (“PVC”). In a particular preferred embodiment, polyolefins can include, for example, polyethylene, polypropylene, ethylene-butene copolymers, and any combination thereof, but preferably polyethylene. In a particular embodiment, exemplary natural or synthetic rubbers can include, for example, latex, uncrosslinked or crosslinked rubbers, granular or ground rubbers, and any combination thereof.

[0084] In certain embodiments, the porous membrane layer preferably comprises a polyolefin, particularly polyethylene. Preferably, the polyethylene is high molecular weight polyethylene (“HMWPE”) (e.g., polyethylene having a molecular weight of at least 600,000). Even more preferably, the polyethylene is ultra-high molecular weight polyethylene (“UHMWPE”) (e.g., polyethylene having a molecular weight of at least 1,000,000, particularly greater than 4,000,000 and most preferably 5,000,000 to 8,000,000, measured by viscometry and calculated using the Margolie equation), a standard load melt index of substantially zero (0) (measured using a 2160 g standard load as specified in ASTM D 1238 (Condition E)), 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 / g and most preferably not less than 3,000 ml / g (measured in a solution of 0.02 g of polyolefin in 100 g of decalin at 130 °C).

[0085] Plasticizer

[0086] In certain embodiments, exemplary processing plasticizers can include processing oils, petroleum, paraffin-based mineral oils, mineral oils, and any combination thereof.

[0087] In some embodiments, the separator has a total residual oil or final oil content in the range of about 0.5% to about 40% by weight, in some embodiments, about 10% to about 30% of residual processing oil, and in some cases, about 20% to about 30% of residual processing oil or residual oil per separator sheet product weight. In some exemplary embodiments, the porous membrane alone can have a residual oil content of about less than or equal to about 10%, while the separator (porous membrane and ribs) can have a residual oil content of about less than or equal to about 20%.

[0088] Filler

[0089] In certain embodiments, exemplary fillers can include: dry, divided silica, precipitated silica, amorphous silica, alumina, talc, fish meal, fish bone meal, and the like, and any combination thereof. In certain preferred embodiments, the filler is one or more of silica, fumed silica, precipitated silica, friable silica, dispersible silica, and / or the like. When forming a lead acid battery separator of the type shown herein, silica having a relatively high level of oil absorptivity and a relatively high level of affinity for a plasticizer (such as mineral oil) becomes desirably dispersible in a mixture of a polyolefin substrate (such as polyethylene) and mineral oil. In some selected embodiments, the filler has an average particle size of 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 silica filler particles is 15 μm - 25 μm. The particle size of the silica filler and / or the surface area of the silica filler contribute to oil absorption. The silica particles in the final product or separator can fall within the above dimensions. However, the initial silica as a raw material can occur as one or more agglomerates and / or aggregates and can have a size of about 200 μm or greater.

[0090] The filler can further reduce the so-called hydration sphere of electrolyte ions, enhancing their transmembrane transport, thereby again reducing the total resistance, or ER, of the battery (such as an enhanced flooded battery) or system.

[0091] One or more fillers can include different species (e.g., polar species such as metals) that facilitate the flow of electrolyte and ions through the separator. Since such separators are used in flooded batteries such as enhanced flooded batteries, this also results in a reduction in the overall resistance.

[0092] Additives / Surfactants

[0093] In certain embodiments, exemplary separators can include one or more performance enhancing additives added to the separator or porous membrane. Performance enhancing additives can be surfactants, wetting agents, colorants, antistatic additives, antimony inhibiting additives, ultraviolet protection additives, antioxidants, and / or the like, and any combination thereof. In certain embodiments, the added surfactant can be an ionic, cationic, anionic, or nonionic surfactant.

[0094] In certain embodiments described herein, a reduced amount of anionic or nonionic surfactant is added to the porous membrane or separator of the present invention. Due to the lower amount of surfactant, desirable characteristics can include reduced total organic carbon ("TOC") and / or reduced volatile organic compounds ("VOC").

[0095] Certain suitable surfactants are nonionic, while other suitable surfactants are anionic. The additive can be a single surfactant or a mixture of two or more surfactants, such as two or more anionic surfactants, two or more nonionic surfactants, or at least one ionic surfactant and at least one nonionic surfactant. Certain suitable surfactants can have an HLB value of less than 6, preferably less than 3. When used together with the separator of the present invention described herein, these certain suitable surfactants can bring further improvements to the separator, and when used in a lead-acid battery, can bring about a reduction in water consumption, a reduction in antimony poisoning, an improvement in cycling, a reduction in floating current, a reduction in floating potential, and / or the like, or any combination thereof. Suitable surfactants include, for example, alkyl sulfates, alkyl aryl sulfonates, alkylphenol-alkylene oxide adducts, soaps, alkyl naphthalene sulfonates, one or more sulfosuccinates (e.g., anionic sulfosuccinates, dialkyl esters of sulfosuccinates), amine compounds (primary, secondary, tertiary amines or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, and surfactants of monoalkyl phosphates and dialkyl phosphate salts. The additive can include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and their mixtures, amine ethoxylates, ethoxylated sorbitan fatty acid esters, silicone-based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphates of fatty acids, and sucrose esters.

[0096] In certain embodiments, the additive can be represented by a compound of formula (I)

[0097]

[0098] wherein

[0099] · R is a linear or non-aromatic hydrocarbon group having from 10 to 4200 carbon atoms, preferably from 13 to 4200 carbon atoms, which may be interrupted by oxygen atoms;

[0100] · R 1 = H, or preferably H, where k = 1 or 2;

[0101] · M is an alkali metal or alkaline earth metal ion, H + or where not all variables M are H simultaneously + ;

[0102] · n = 0 or 1;

[0103] · m = 0 or an integer from 10 to 200; and

[0104] · x = 1 or 2.

[0105] In the compounds according to formula (I), the ratio of oxygen atoms to carbon atoms is in the range from 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 equal to 0.

[0106] The term non-aromatic hydrocarbon radical means a radical which does not contain an aromatic group or which itself represents an aromatic group. The hydrocarbon radical may be interrupted by oxygen atoms (i.e., contain one or more ether groups).

[0107] R is preferably a straight-chain or branched-chain aliphatic hydrocarbon radical which may be interrupted by oxygen atoms. Saturated, non-crosslinked hydrocarbon radicals are very particularly preferred. However, as noted above, in certain embodiments, R may be aromatic-ring-containing.

[0108] By using the compounds of formula (I) in the production of battery separators, the separators can be effectively protected against oxidative damage.

[0109] Battery separators containing the compounds according to formula (I) are preferred, wherein:

[0110] · R is a hydrocarbon radical having from 10 to 180, preferably from 12 to 75 and very particularly preferably from 14 to 40 carbon atoms, which may be interrupted by from 1 to 60, preferably from 1 to 20 and very particularly preferably from 1 to 8 oxygen atoms, particularly preferably a radical of the formula R 2 —[(OC2H4) p (OC3H6) q —, wherein:

[0111] οR 2 is an alkyl radical having from 10 to 30 carbon atoms, preferably from 12 to 25, particularly preferably from 14 to 20 carbon atoms, wherein R 2 may be linear or non-linear, for example contain an aromatic ring;

[0112] οP is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; and

[0113] οq is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4;

[0114] οwherein the sum of p and q is from 0 to 10, in particular from 0 to 4, is very particularly preferred;

[0115] · n = 1; and

[0116] · m = 0.

[0117] The radical of the formula R 2 —[(OC2H4) p (OC3H6) qIt should be understood to also include those compounds in which the group sequences in the square brackets are different from those shown. For example, the free radicals in the brackets are formed by alternating (OC2H4) and (OC3H6) groups, and the compounds according to the invention are suitable.

[0118] It has been shown that additives in which R 2 is a straight-chain or branched-chain alkyl group having 10 to 20, preferably 14 to 18 carbon atoms are particularly advantageous. Preferably, OC2H4 represents OCH2CH2, and OC3H6 represents OCH(CH3)2 and / or OCH2CH2CH3.

[0119] As preferred additives, mention may be made in particular of alcohols (p = q = 0; m = 0), primary alcohols are 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), and ethoxylates of primary alcohols are preferred. Fatty alcohol alkoxylates can be obtained, for example, by reacting the corresponding alcohols with ethylene oxide or propylene oxide.

[0120] It has been shown that additives of the m = 0 type that are insoluble or only poorly soluble in water and sulfuric acid are particularly advantageous.

[0121] Also preferred are additives containing compounds according to formula (I), wherein:

[0122] · R is an alkyl group having 20 to 4200, preferably 50 to 750, and very particularly preferably 80 to 225 carbon atoms;

[0123] · M is an alkali metal or alkaline earth metal ion, H + or especially alkali metal ions such as Li + , Na + and K + or H + where not all variables M are H simultaneously + ;

[0124] · n = 0;

[0125] · m is an integer from 10 to 200; and

[0126] · x = 1 or 2.

[0127] Salt additives

[0128] In certain embodiments, suitable additives can particularly include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers, in which the acid groups are at least partially (such as preferably 40% and particularly preferably 80%) neutralized. The percentage refers to the number of acid groups. Very particularly preferred is poly(meth)acrylic acid present entirely in salt form. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium (NR4, where R is hydrogen or a carbon functional group). Poly(meth)acrylic acid can include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acid is preferred, particularly polyacrylic acid having an average molar mass Mw of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, and very 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 (Fikentscher constant) of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution.

[0129] Also suitable are copolymers of (meth)acrylic acid, particularly copolymers that, in addition to (meth)acrylic acid, contain ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and / or 2-ethylhexyl acrylate as comonomers. Copolymers containing at least 40% by weight, preferably at least 80% by weight, of (meth)acrylic acid monomers are preferred, this percentage being based on the monomer or the acid form of the polymer.

[0130] For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides, such as potassium hydroxide and especially sodium hydroxide, are particularly suitable. Additionally, coatings and / or additives for reinforcing the separator can include, for example, metal alkoxides. By way of example only (not intended to be limiting), the metal in the metal alkoxide can be Zn, Na, or Al, and by way of example only, the metal alkoxide can be sodium ethoxide.

[0131] In some embodiments, the microporous polyolefin porous membrane can include a coating on one or both sides of such a layer. Such coatings can include surfactants or other materials. In some embodiments, the coating can include, for example, one or more materials described in U.S. Patent Publication No. 2012 / 0094183, the content of which is incorporated herein by reference. For example, such a coating can reduce the overcharge voltage of the battery system, thereby extending battery life with less grid corrosion and preventing drying out and / or water consumption.

[0132] Ratio

[0133] In certain selected embodiments, the membrane can be prepared by combining by weight about 5 - 15% polymer (in some cases, about 10% polymer), about 10 - 75% filler (in some cases, about 30% filler), and about 10 - 85% processing oil (in some cases, about 60% processing oil). In other embodiments, the filler content is reduced while 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) can be approximately (or can be between approximately 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, 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. For operating performance and desired separator characteristics such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flatness, etc., the amounts of filler, oil, polymer (such as polyethylene) are all balanced.

[0134] According to at least one embodiment, the porous membrane can include UHMWPE mixed with processing oil and precipitated silica. According to at least one embodiment, the microporous membrane can include UHMWPE mixed with processing oil, additives and precipitated silica. The mixture can also include small amounts of other additives or reagents common in the separator field (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants and / or the like and any combination thereof). In certain cases, the microporous polymer layer can be a homogeneous mixture of 8 to 100% volume of polyolefin, 0 to 40% volume of plasticizer, and 0 to 92% volume of inert filler material. 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 in imparting porosity to the battery separator.

[0135] Microporous membranes made according to the present invention and containing polyethylene and a filler (such as silica) typically have a residual oil content; in some embodiments, such residual oil content ranges from about 0.5% to about 40% of the total weight of the separator membrane (in some cases, about 10 - 40% of the total weight of the separator membrane, and in some cases, about 20 - 40% of the total weight). In certain selected embodiments herein, some to all of the residual oil content in the separator can be replaced by adding more performance enhancing additives, such as surfactants, such as surfactants having a hydrophilic - lipophilic balance (“HLB”) less than 6 or such as nonionic surfactants. For example, performance enhancing additives such as surfactants, such as nonionic surfactants, can constitute from 0.5% up to all of the residual oil content of the total weight of the microporous separator membrane (e.g., up to 20% or 30% or even 40%), thereby partially or completely replacing the residual oil in the separator membrane.

[0136] Manufacture

[0137] In some embodiments, an exemplary porous membrane can be prepared by mixing the components in an extruder. For example, about 30 wt% silica, about 10 wt% UHMWPE, and about 60% processing oil can be mixed in an extruder. The exemplary microporous membrane can be prepared by passing the components through a heated extruder, passing the extrudate from the extruder through a die and into a gap formed by two heated presses or calendering units or rolls to form a continuous web. The calendering rolls also determine the base web thickness TBASE and / or the back web thickness TBACK. A substantial amount of the processing oil can be extracted from the web by using a solvent. Then, the web can be dried and cut into strips of a predetermined width and then wound onto a roll. Alternatively, or additionally, the presses or calendering rolls can be engraved with various groove patterns to impart ribs, grooves, textured areas, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, discontinuous ribs, angled ribs, linear ribs or curved or sinusoidal ribs, protrusions, depressions, and / or the like, and any combination thereof, extending into or out of the microporous membrane of the separator.

[0138] Manufacture with surfactant

[0139] In certain embodiments, optional additives or reagents (such as surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like and any combination thereof) can also be mixed with the other components in an extruder. Then, the microporous membrane according to the present disclosure can be extruded into a sheet or web shape and completed in substantially the same manner as described above.

[0140] In certain embodiments, in addition to being added to the extruder, or alternatively, one or more additives can be applied to the separator porous membrane, for example, when the separator is completed (e.g., after most of the processing oil has been extracted). According to certain preferred embodiments, the additive or additive solution (such as an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for applying non-thermally stable additives and additives that are soluble in the solvent used for extracting the processing oil. Particularly suitable solvents for the additives according to the present invention are low molecular weight alcohols such as methanol and ethanol, and mixtures of these alcohols with water. The application can be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or on both sides. The application can also be carried out in a solvent bath during the extraction of the pore former (such as the processing oil). In certain selected embodiments, a portion of the performance enhancing additive such as a surfactant coating or the performance enhancing additive (or both) added to the extruder before the separator is manufactured can combine with the antimony in the battery system and can deactivate it and / or form a compound with it and / or cause it to fall into the battery sludge and / or prevent its deposition on the negative electrode.

[0141] In certain embodiments, the additive (such as a nonionic surfactant, an anionic surfactant, or a mixture thereof) can be at least 0.5 g / m 2 、1.0 g / m 2 、1.5 g / m 2 、2.0 g / m 2 、2.5 g / m 2 、3.0 g / m 2 、3.5 g / m 2 、4.0 g / m 2 、4.5 g / m 2 、5.0 g / m 2 、5.5 g / m 2 、6.0 g / m 2 、6.5 g / m 2 、7.0 g / m 2 、7.5 g / m 2 、8.0 g / m 2 、8.5 g / m 2 、9.0 g / m 2 、9.5 g / m 2 or 10.0 g / m 2 or even up to about 20.0 g / m 2 of density or addition level. The additive can be present on the separator at 0.5 - 15 g / m 2 、0.5 - 10 g / m 2 、1.0 - 10.0 g / m 2 、1.5 - 10.0 g / m 2, 2.0 - 10.0 g / m 2 , 2.5 - 10.0 g / m 2 , 3.0 - 10.0 g / m 2 , 3.5 - 10.0 g / m 2 , 4.0 - 10.0 g / m 2 , 4.5 - 10.0 g / m 2 , 5.0 - 10.0 g / m 2 , 5.5 - 10.0 g / m 2 , 6.0 - 10.0 g / m 2 , 6.5 - 10.0 g / m 2 , 7.0 - 10.0 g / m 2 , 7.5 - 10.0 g / m 2 , 4.5 - 7.5 g / m 2 , 5.0 - 10.5 g / m 2 , 5.0 - 11.0 g / m 2 , 5.0 - 12.0 g / m 2 or a density or addition level between 5.0 - 15.0 g / m 2 exists between the density or addition levels.

[0142] The application can also be carried out by impregnating the battery separator in an additive or an additive solution (solvent bath addition) and removing the solvent if necessary (e.g., by drying). In this way, the application of the additive can be combined, for example, with the extraction often employed during membrane production. Other preferred methods are spraying the surface of the separator with the additive, dip - coating, roll - coating, or curtain - coating one or more additives on the surface of the separator.

[0143] In the specific embodiments described herein, a reduced amount of anionic or non - ionic surfactant is added to the separator of the invention. In this case, the desired properties can include reduced total organic carbon and / or reduced volatile organic compounds (due to the smaller amount of surfactant), and the desired inventive separator according to this embodiment can be produced.

[0144] Manufacture / Thickness

[0145] As described above, a press or calender can be engraved to impart ribs, grooves, textured areas, serrated protrusions, serrated ribs, stack - like protrusions or stack - like ribs, discontinuous ribs, angled ribs, linear ribs or curved or sinusoidal ribs, protrusions, depressions, and / or the like or any combination thereof that extend into or from the microporous membrane.

[0146] In some embodiments, the porous separator membrane may have a backsheet thickness ranging from about 50 μm - 1.0 mm and 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. 背网 (Although in certain embodiments, a very thin and flat backsheet thickness of 50 μm is provided 背网 , for example, thick between 50 μm and 75 μm). In certain embodiments, the backsheet thickness 背网 can be less than or equal to about 125 μm ± 75 μm.

[0147] In certain embodiments, the porous membrane may have a base web thickness TBASE ranging from about 50 μm - 1.0 mm, about 50 μm - 750 μm, about 100 μm - 750 μm, about 200 μm - 750 μm, about 200 μm - 500 μm, about 150 μm - 500 μm, about 250 μm - 500 μm, about 250 μm - 400 μm, or about 250 μm - 350 μm. In certain embodiments, the base web thickness TBASE can be less than or equal to about 200 μm ± 35 μm.

[0148] Puncture resistance

[0149] In certain selected embodiments, an exemplary separator may be characterized by enhanced puncture resistance. For example, a puncture resistance of about 9 N or higher, 9.5 N or higher, 10 N or higher, 10.5 N or higher, 11 N or higher, 11.5 N or higher, 12 N or higher, 12.5 N or higher, 13 N or higher, 13.5 N or higher, 14 N or higher, 14.5 N or higher, 15 N or higher, 15.5 N or higher, 16 N or higher, 16.5 N or higher, 17 N or higher, 17.5 N or higher, 18 N or higher, 18.5 N or higher, 19 N or higher, 19.5 N or higher, or 20 N or higher. In certain embodiments, an exemplary separator may preferably be defined by an average puncture resistance of about 9 N - 20 N or higher, or more preferably about 11 N - 20 N or higher.

[0150] Such as Figure 5As commonly depicted, puncture resistance can be measured as the force required to pierce a porous membrane using tip 200. While tip 200 pierces the membrane, the puncture substrate supporting the porous membrane can typically be described as having a straight hole with a diameter of 6.5 mm and a depth of 10 mm. The travel limit of the tip can be about 4 mm - 8 mm below the puncture base surface. The puncture tip 200 linearly moves into the membrane at a rate of approximately 5 mm / s.

[0151] Electrical resistance

[0152] In certain selected embodiments, exemplary separators exhibit reduced electrical resistance. For example, the impedance is not greater than about 200 mΩ·cm 2 、180 mΩ·cm 2 、160 mΩ·cm 2 、140 mΩ·cm 2 、120 mΩ·cm 2 、100 mΩ·cm 2 、80 mΩ·cm 2 、60 mΩ·cm 2 、50 mΩ·cm 2 、40 mΩ·cm 2 、30 mΩ·cm 2 or 20 mΩ·cm 2 . In certain selected embodiments, exemplary separators can have a preferred electrical resistance of 40 mΩ·cm 2 -25 mΩ·cm 2 or lower.

[0153] To test a sample separator for ER test evaluation according to the present invention, it must first be prepared. To this end, the sample separator is preferably immersed in a demineralized water bath, and then the water is boiled. After 10 minutes in the boiling demineralized water bath, the separator is removed. After removal, the excess water is shaken off the separator and then placed in a sulfuric acid bath having a specific gravity of 1.280 at 27°C ± 1°C. The separator is soaked in the sulfuric acid bath for 20 minutes. After that, the separator is ready for electrical resistance testing.

[0154] Flexural stiffness

[0155] In certain selected embodiments, exemplary separators can be characterized by having enhanced flexural stiffness in the transverse direction. Although not wishing to be bound by theory, it is believed that enhanced flexural stiffness in the transverse direction improves the processability of the separator during lead-acid battery manufacturing.

[0156] For example, one embodiment of the separator may have a flexural stiffness of about 20 mN or higher, 21 mN or higher, 22 mN or higher, 23 mN or higher, 24 mN or higher, 25 mN or higher, 26 mN or higher, 27 mN or higher, 28 mN or higher, 29 mN or higher, 30 mN or higher, 31 mN or higher, 32 mN or higher, 33 mN or higher, 34 mN or higher, 35 mN or higher, 36 mN or higher, 37 mN or higher, 38 mN or higher, 39 mN or higher, 40 mN or higher, 41 mN or higher, 42 mN or higher, 43 mN or higher, 44 mN or higher, 45 mN or higher. In a particular embodiment, an exemplary separator may be defined by a puncture resistance of about 20 mN - 40 mN or higher, or more preferably about 25 mN - 45 mN or higher.

[0157] The flexural stiffness in the lateral direction can be measured as the force required to bend the sample. Figure 6 A test device for measuring the flexural stiffness is shown. To measure this value, it may be preferred to cut the separator sample into a rectangle of 150 mm by 10.0 mm. For the test, the 150 mm edge of the sample is clamped along the length. A force is applied at a bending length D of 5 mm. The flexural stiffness is determined by the force required to bend the sample to a bending angle α of 30°. The bending angle α is determined by a plane that passes through the sample between the clamping and the application of the force and is the same as the plane at the end of the test.

[0158] Oxidation stability

[0159] In a particular selected embodiment, an exemplary separator may be characterized by improved and higher antioxidant properties. The antioxidant property is measured by the elongation in the lateral direction of a sample separator specimen after long-term exposure to the lead-acid battery electrolyte. For example, an exemplary separator may have an elongation of about 100% or higher, 150% or higher, 200% or higher, 250% or higher, 300% or higher, 350% or higher, 400% or higher, 450% or higher, or 500% or higher at 40 hours. In a particular embodiment, an exemplary separator may have a preferred antioxidant property or elongation of about 100% or higher at 40 hours. Additionally, an exemplary separator may have an elongation of about 200% or higher, 250% or higher, 300% or higher, 350% or higher, 400% or higher, 450% or higher, or 500% or higher at 20 hours. In a particular embodiment, an exemplary separator may have a preferred antioxidant property or elongation of about 200% or higher at 20 hours.

[0160] To test the antioxidant property of the sample, first, a sample specimen 400 of the exemplary separator is cut into as Figure 7Athe shape commonly described therein. Then the sample 400 is placed in a sample holder as commonly shown in Figure 7B a sample holder as commonly shown therein.

[0161] At time = 0 hours, the percent elongation at break of the first set of samples for the drying test is measured. The elongation rate is based on the 50 mm distance measured between point A and point B in Figure 7A therein. For example, if points A and B are stretched to 300% of the distance, the final distance between A and B will be 150 mm.

[0162] The elongation rate test is designed to simulate exposure to the electrolyte in a cycling battery over a long period of time in a shortened time period. First, the sample 400 is completely immersed in isopropyl alcohol, drained, and then immersed in water for 1 - 2 seconds. After that, the sample is immersed in the electrolyte solution. This solution is prepared by sequentially adding 360 ml of sulfuric acid with a specific gravity of 1.28, 35 ml of sulfuric acid with a specific gravity of 1.84, and then 105 ml of 35% hydrogen peroxide. The solution is maintained at 80°C, and the sample is immersed in the solution for a long time. The elongation rate of the sample can be measured at fixed time intervals (such as 20 hours, 40 hours, 60 hours, 80 hours, etc.). To test at these intervals, the sample 400 is removed from the 80°C electrolyte bath and placed under gently flowing warm water until the acid is removed. After that, the elongation rate can be tested.

[0163] According to at least selected embodiments, the present disclosure or invention is directed to improved battery separators, low ER or high conductivity separators, improved lead - acid batteries such as flooded lead - acid batteries, high conductivity batteries, and / or improved vehicles including such batteries and / or methods of making or using such separators or batteries and / or combinations thereof. According to at least specific embodiments, the present disclosure or invention is directed to an improved lead - acid battery incorporating an improved separator, which exhibits increased conductivity.

[0164] Examples

[0165] Table 1 details the parameters of an exemplary inventive battery separator according to the present disclosure.

[0166] Table 1

[0167] Performance Value <![CDATA[Base net thickness 底网 (μm)]]> 200±35 <![CDATA[Back net thickness Thickness back 网 (μm)]]> 125±75 <![CDATA[NCR Height Neg (μm)]]> 50-75 Puncture Resistance (N) ≥12.5 <![CDATA[Resistance (mΩ·cm 2 )]]> ≤40 CMD Elongation Rate (%) ≥200 CMD Bending Stiffness (mN) ≥35 Antioxidant Property - 40h (%) ≥200 Antioxidant Property - 20h (%) ≥200 <![CDATA[Grammage (g / m 2 )]]> ≤130 Total Oil Content (%) ≤20 Back Mesh Oil Content (%) ≥10 Ash Content (%) 67.0±2.5 Porosity in Water (%) 64±4

[0168] Table 2 represents the parameters of an exemplary inventive battery separator according to the present disclosure. Improved separator #1 represents the first attempt in creating the separator of the present invention, and improved separator #2 represents an exemplary separator resulting from the finishing process.

[0169] Table 2

[0170]

[0171] Table 3 details the comparison between an exemplary improved separator #2 and control separators #1 and #2 (both commercially available lead-acid battery separators).

[0172] Table 3

[0173]

[0174] Conclusion

[0175] The improved separator is useful in various batteries, especially in lead-acid batteries and 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 golf cart (sometimes called golf car) batteries, or in other deep cycle applications such as solar or wind energy batteries.

[0176] In addition, the inventive battery separator disclosed and described herein provides an improved deep cycle battery in which it is used at a more consistent and lower end-of-charge current (EOC). Maintaining a lower EOC current indicates that the improved battery described herein exhibits suppression of antimony poisoning. For example, as a new deep cycle lead-acid battery ages, there is more antimony in the battery, which means that the EOC current may increase over the life of the battery, thereby increasing the water consumption of the battery and thus reducing the cycle performance of the battery over its entire life. 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.

[0177] Furthermore, the improved battery separator described herein also provides a deep cycle flooded lead-acid battery that shows a reduced floating charge current at steady state potential relative to a battery made with a previously known separator; shows a reduction in the voltage and / or energy required to recharge a battery operating in deep cycle relative to a deep cycle battery made with a previously known separator; shows generally improved voltage control relative to a battery made with a previously known separator; and / or shows a reduction in grid corrosion relative to a battery made with a previously known separator.

[0178] In a selected embodiment of the present invention, the lead-acid battery separator can be provided with a basis weight of about 130 g / m 2 or less and a bending stiffness in the transverse direction greater than or equal to about 25 mN.

[0179] In certain other selected embodiments of the present invention, the lead-acid battery separator can be provided with a transverse stiffness of less than or equal to about 25 mN and a backsheet thickness of less than or equal to about 125 μm.

[0180] In some aspects of the present invention, the separator can be provided with a resistance of less than or equal to about 40 mΩ·cm2 a resistance, an average puncture resistance greater than or equal to about 11.0 N, an antioxidant property greater than or equal to 200% at 20 hours, an antioxidant property greater than or equal to about 100% at 40 hours, a back web density less than or equal to about 125 μm, a residual oil content less than or equal to about 20%, and a porous membrane having a residual oil content greater than or equal to about 10%.

[0181] In other aspects of the present invention, the lead acid battery separator may have at least one set of ribs, where the at least one set of ribs is at least one selected from the following: solid ribs, discontinuous ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the transverse direction of the porous membrane, cross-cut ribs extending substantially in the transverse direction of the porous membrane, cross ribs extending substantially in the transverse direction of the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or discontinuous serrated manner, grooves, channels, textured areas, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0182] In a selected embodiment, the separator may have a first set of ribs extending from a first back web surface, having a first rib height measured from the first back web surface; a second set of ribs extending from a second back web surface and substantially orthogonal to the first set of ribs, having a second rib height measured from the second back web surface; and a bottom web thickness less than or equal to about 200 μm. The second set of ribs may have a height less than or equal to about 75 μm and a back web thickness less than or equal to about 100 μm.

[0183] An exemplary separator may have a total thickness between about 400 μm and about 2.0 mm.

[0184] In a specific exemplary embodiment, the lead acid battery separator may have a first set of ribs, which is at least one from the following: solid ribs, discontinuous ribs, discrete discontinuous ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the transverse direction of the porous membrane, cross-cut ribs extending substantially in the transverse direction of the porous membrane, cross ribs extending substantially in the transverse direction of the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or discontinuous serrated manner, grooves, channels, textured areas, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0185] In other selected embodiments, the lead acid battery separator may have a second set of ribs, which are at least one of the following: solid ribs, intermittent ribs, discrete intermittent ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the transverse direction of the porous membrane, cross-cut ribs extending substantially in the transverse direction of the porous membrane, cross ribs extending substantially in the transverse direction of the porous membrane, serrated protrusions, serrated ribs, stack-like protrusions or stack-like ribs, curved or sinusoidal ribs, arranged in a solid or intermittent serrated manner, grooves, channels, textured areas, protrusions, depressions, porous, non-porous, micro ribs or cross micro ribs, and combinations thereof.

[0186] In selected embodiments, the present invention provides a lead acid battery equipped with a separator as fully described herein. The battery can be a flat plate battery, a tubular battery, a flooded lead acid battery, an enhanced flooded lead acid battery, a deep cycle battery, an absorbed glass mat battery, a tubular battery, an inverter battery, a vehicle battery, a starting lighting ignition (“SLI”) battery, an idle start-stop (“ISS”) battery, an automotive battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric vehicle battery, an electric rickshaw battery, an electric bicycle battery, or a marine battery.

[0187] The battery can operate in a partially charged state, during movement, or at rest, or in all of the above cycles.

[0188] In certain selected embodiments, the present invention provides a vehicle equipped with a lead acid battery, the lead acid battery being equipped with a separator as fully described herein. The vehicle can be an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart, an idle start-stop vehicle, a hybrid electric vehicle, an electric vehicle, an electric rickshaw, an electric bicycle, or a marine vessel.

[0189] This document presents, claims, or describes new or improved separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, methods, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, primary cells, systems, and / or batteries; new or improved battery separators for enhanced flooded batteries; methods, systems, and battery separators having reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof; improved separators for enhanced flooded batteries, wherein the separator has reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, or any combination thereof; provided are separators that include or exhibit reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof; the separators are equipped for use in batteries for flat batteries, tubular batteries, vehicle SLI and HEVISS applications, deep cycle applications, golf cars or golf carts, and electric rickshaw batteries, batteries operating in a partial state of charge (“PSOC”), inverter batteries, and storage batteries for renewable energy, and any combination thereof; and / or the like.

[0190] According to at least selected embodiments, aspects, or objectives, disclosed or provided herein are new or improved separators, battery separators, enhanced flooded battery separators, batteries, primary cells, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, primary cells, and / or batteries. According to at least specific embodiments, the present disclosure or invention is directed to new or improved battery separators for enhanced flooded batteries. Additionally, disclosed herein are methods, systems, and battery separators having reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least particular embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries, wherein the separator has reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, or any combination thereof. According to at least specific embodiments, provided are separators that include or exhibit reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant properties, reduced separator thickness, reduced basis weight, and any combination thereof. According to at least specific embodiments, the separators are provided for use in batteries for flat batteries, tubular batteries, vehicle SLI and HEVISS applications, deep cycle applications, golf cars or golf carts, and electric rickshaw batteries, batteries operating in a partial state of charge (“PSOC”), inverter batteries, and storage batteries for renewable energy, and any combination thereof.

[0191] According to at least selected embodiments, the present disclosure or invention is directed to new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, methods, and / or vehicles using them and / or methods of manufacturing and / or using such separators, battery separators, enhanced flooded battery separators, batteries, primary cells, systems, and / or vehicles using the same components as described above. According to at least specific embodiments, the present disclosure or invention is directed to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, vehicle batteries such as automotive starting lighting ignition ("SLI") batteries, batteries for automotive idle start-stop ("ISS") applications such as those used in hybrid electric vehicles, and / or enhanced flooded batteries ("EFB"), and / or improved methods of manufacturing and / or using such improved separators, primary cells, batteries, systems, vehicles, and / or the like. According to at least specific embodiments, the present disclosure or invention is directed to improved separators for enhanced flooded batteries and / or improved methods of manufacturing, testing, and / or using batteries having such improved separators. According to at least selected embodiments, the present disclosure or invention is directed to separators, particularly for enhanced flooded batteries, having reduced separator electrical resistance ("ER"), reduced separator thickness, increased separator puncture strength, enhanced separator cross machine direction ("CMD") stiffness, improved separator oxidation resistance, reduced separator basis weight, increased separator wettability, or any combination thereof. Additionally, disclosed herein are methods, systems, and battery separators for use in at least enhanced flooded batteries to extend battery life, reduce water consumption, increase wettability, reduce internal resistance, and / or improve uniformity. 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, reduced resistance, reduced thickness, increased puncture strength, increased CMD stiffness, improved oxidation resistance, reduced basis weight, or any combination thereof.

[0192] According to at least certain possible preferred embodiments, aspects or purposes, provided are membranes, separator membranes or separators having a new structure and / or an improved combination of properties. Also provided are related batteries, methods and systems. In certain embodiments, provided are new or improved separators, battery separators, enhanced flooded battery separators, batteries, primary cells and / or methods of manufacturing and / or using such separators, battery separators, enhanced flooded battery separators, primary cells and / or batteries. Additionally, disclosed herein are methods, systems and battery separators having a reduced ER, increased puncture strength, enhanced separator CMD stiffness, improved antioxidant resistance, reduced separator thickness, reduced basis weight and any combination thereof. According to at least certain embodiments, the provided separators are used in battery applications for flat batteries, tubular batteries, vehicle SLI and HEV ISS applications, deep cycle applications, golf carts or golf cars and electric rickshaw batteries, batteries operating in a partial state of charge (“PSOC”), inverter batteries and storage batteries for renewable energy and any combination thereof.

[0193] According to at least certain possible preferred embodiments, aspects or purposes, provided or disclosed are:

[0194] A lead-acid battery separator comprising:

[0195] At least one membrane having a basis weight of about 140 g / m 2 or less, and

[0196] A flexural stiffness in the transverse direction of greater than or equal to about 25 mN.

[0197] The above separator, wherein the membrane has a basis weight of about 135 g / m 2 or less, and

[0198] A flexural stiffness in the transverse direction of greater than or equal to about 25 mN.

[0199] The above separator, wherein the membrane has a basis weight of about 130 g / m 2 or less, and

[0200] A flexural stiffness in the transverse direction of greater than or equal to about 25 mN.

[0201] The above separator, wherein the membrane has a resistance of less than or equal to about 40 mΩ·cm 2 and an average puncture resistance of greater than or equal to about 9.0 N.

[0202] The above separator, wherein the membrane has a resistance of less than or equal to about 40 mΩ·cm 2 of resistance.

[0203] The above separator, wherein the membrane has an average puncture resistance of greater than or equal to about 10.0 N.

[0204] The above-mentioned separator, wherein the membrane has an average puncture resistance greater than or equal to about 12.0 N.

[0205] The above-mentioned separator, wherein the membrane has an average puncture resistance greater than or equal to about 14.0 N.

[0206] Without departing from the spirit and essential characteristics of the present invention, the present invention may be implemented in other forms. Therefore, when indicating the scope of the present invention, reference should be made to the appended claims rather than the foregoing description.

[0207] The foregoing written description of the structures and methods has been presented only for purposes of illustration. Examples, including the best mode, are used to disclose exemplary embodiments and also to enable those skilled in the art to practice the invention, including making and using any devices or systems and performing any associated methods. These examples are not intended to be exhaustive or to limit the invention to the precise steps and / or forms disclosed, and many modifications and variations are possible in light of the above teachings. The features described herein may be combined in any combination. The steps of the methods described herein may be performed in any physically possible order. 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 such other embodiments have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims, then such other embodiments are intended to be within the scope of the claims.

[0208] The scope of the compositions and methods of the appended claims is not limited by the specific compositions and methods described herein, which are intended to be illustrative of several aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various variations of the compositions and methods, in addition to those shown and described herein, are also intended to fall within the scope of the appended claims. Moreover, although only specific representative compositions and method steps disclosed herein are specifically described, other combinations of compositions and method steps, even if not specifically recited, are also intended to fall within the scope of the appended claims. Thus, combinations of steps, elements, components, or ingredients may be explicitly or implicitly mentioned herein, but other combinations of steps, elements, components, and ingredients are included even if not explicitly stated.

[0209] As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations by use of the antecedent "about", it will be understood that the particular value forms another embodiment. It should be further understood that each end point of each range is significant both in relation to the other end point and independently of the other end point. "Optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0210] Throughout the specification and claims of this specification, the word "comprising" and variations of the word, such as the participle form "comprising" and the singular form "comprises", 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" may be used in place of "comprising" and "including" to provide more particular embodiments of the invention, and are also disclosed. "Exemplary" means "an example of...", and is not intended to convey an indication of a preferred or ideal embodiment. Likewise, "such as" is not restrictive, but is for explanatory or illustrative purposes.

[0211] Unless stated otherwise, all numbers expressing geometric shapes, dimensions, etc. used in the specification and claims should be understood at least not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, and should be interpreted in accordance with the number of significant digits and the normal rounding-off method.

[0212] Unless otherwise defined, 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 pertains. Publications and the materials cited therein are specifically incorporated by reference.

[0213] In addition, the inventions illustratively disclosed herein may be suitably practiced in the absence of any element not specifically disclosed herein.

Claims

1. A lead-acid battery separator, which includes a porous membrane and has a back grid; when placed in a battery, the back grid has a positive electrode surface facing the positive electrode and a negative electrode surface facing the negative electrode; the positive electrode surface has positive electrode ribs extending along the processing direction, and the negative electrode surface has negative electrode ribs extending along the direction across the processing direction; the positive electrode ribs in the processing direction extend from the positive electrode surface of the back grid by 8 μm to 1 mm, and the negative electrode ribs in the direction across the processing direction extend from the negative electrode surface of the back grid by 50 - 75 μm; the spacing between the negative electrode ribs in the processing direction is more compact than the spacing between the positive electrode ribs in the processing direction.

2. The lead-acid battery separator according to claim 1, wherein, the battery separator has an antioxidant property of 200% or higher for 40 hours; the battery separator has a puncture resistance of 9 N or greater, and the battery separator has a puncture resistance of 12 N or greater; and / or the battery separator has a transverse bending stiffness of 20 mN or greater, or 25 mN or greater.

3. The lead-acid battery separator according to claim 1, wherein, The porous membrane has ribs; preferably, the porous membrane comprises one selected from the following: ribs, grooves, textured areas, serrated protrusions or serrated ribs, solid ribs, stack-like protrusions or stack-like ribs, discontinuous ribs, angled ribs, linear ribs, curved or sinusoidal ribs, ribs arranged in a serrated manner, raised or raised-like ribs, depressions, negative cross ribs, and combinations thereof; the porous membrane comprises negative side cross ribs; and / or, the lead-acid battery separator further comprises a fiber mat.

4. The lead-acid battery separator according to claim 1, wherein, the porous membrane is selected from: polyolefin, polyethylene, polypropylene, rubber, polyvinyl chloride, phenolic resin, cellulose, synthetic wood pulp, glass fiber, synthetic fiber, natural rubber, synthetic rubber, latex, and any combination thereof; the porous membrane is polyethylene; the porous membrane contains particulate fillers, and the particulate fillers are selected from: dry and finely divided silica, precipitated silica, alumina, talc powder, and combinations thereof; and / or the porous membrane contains additives; the additives are selected from: non-ionic surfactants, ionic surfactants, wetting agents, colorants, antistatic additives, ultraviolet protection additives, antioxidants, and combinations thereof.

5. A lead-acid battery, which includes the lead-acid battery separator according to claim 1.

6. The lead-acid battery according to claim 5, wherein, The lead-acid battery is selected from: flat battery, flooded lead-acid battery, enhanced flooded lead-acid battery, deep cycle battery, absorbed glass mat battery, tubular battery, inverter battery, vehicle battery, starting lighting ignition (SLI) battery, idle start-stop (ISS) battery, automotive battery, truck battery, motorcycle battery, all-terrain vehicle battery, forklift battery, golf cart battery, hybrid electric vehicle battery, electric vehicle battery, electric rickshaw battery, electric bicycle battery.

7. The lead-acid battery according to claim 5, wherein, The lead-acid battery operates in a partially charged state; the lead-acid battery operates during movement; or, the lead-acid battery operates while stationary.

8. A system, which includes the lead-acid battery according to claim 6, and the lead-acid battery operates in a partially charged state.

9. A lead-acid battery separator, which includes: a porous membrane, which is a back grid; A first set of ribs extending from a first back web surface and having a first rib height measured from said first surface; A second set of ribs extending from a second back web surface and having a second rib height measured from said second surface; the range of the second rib height is 50 - 75 μm; the back web thickness is 125 ± 75 μm, The porous membrane simultaneously has a basis weight of up to 130 g / m 2 , a resistance of up to 40 mΩ·cm 2 , and a puncture resistance of at least 12.5 N.

10. The lead acid battery separator according to claim 9, wherein, The battery separator has a transverse bending stiffness of 25 mN or greater; The battery separator has an antioxidant property of 200% or higher for 40 hours; The porous membrane is selected from: polyolefin, polyethylene, polypropylene, rubber, polyvinyl chloride, phenolic resin, cellulose, synthetic wood pulp, glass fiber, synthetic fiber, natural rubber, synthetic rubber, latex, and any combination thereof; The porous membrane is polyethylene; The porous membrane contains particulate fillers selected from: dry ground silica, precipitated silica, alumina, talc powder, and combinations thereof; and / or The porous membrane contains additives selected from: non - ionic surfactants, ionic surfactants, wetting agents, colorants, antistatic additives, ultraviolet protection additives, antioxidants, and combinations thereof.

11. The lead-acid battery separator according to claim 9, wherein, The porous membrane contains one selected from the following: ribs, grooves, textured areas, serrated protrusions, serrated ribs, solid ribs, stack - like protrusions or stack - like ribs, discontinuous ribs, angled ribs, linear ribs, curved or sinusoidal ribs, ribs arranged in a serrated manner, raised or raised - like ribs, depressions, transverse ribs facing the negative electrode, and combinations thereof; the porous membrane contains negative - side cross ribs; and / or The lead acid battery separator further comprises a fiber mat.

12. A lead acid battery comprising the lead acid battery separator according to claim 9.

13. The lead-acid battery according to claim 12, wherein, The lead acid battery is selected from: flat plate batteries, flooded lead acid batteries, enhanced flooded lead acid batteries, deep - cycle batteries, absorbed glass mat batteries, tubular batteries, inverter batteries, vehicle batteries, starting lighting ignition (SLI) batteries, idle start - stop (ISS) batteries, automotive batteries, truck batteries, motorcycle batteries, all - terrain vehicle batteries, forklift truck batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric bicycle batteries.

14. The lead-acid battery according to claim 12, wherein, The lead acid battery operates in a partially charged state; the lead acid battery operates during movement; or, the lead acid battery operates while stationary.

15. A system comprising the lead acid battery according to claim 12.

16. The system according to claim 15, wherein The lead acid battery operates in a partially charged state; or, the lead acid battery is the lead acid battery according to claim 13.

17. The system according to claim 15, wherein, The vehicle is selected from: automobiles, trucks, motorcycles, all - terrain vehicles, forklift trucks, golf carts, hybrid electric vehicles, electric vehicles, electric rickshaws, electric bicycles, and combinations thereof.

18. A lead-acid battery separator that simultaneously has: a basis weight of up to 130 g / m 2 , a resistance of up to 40 mΩ·cm 2 , and a puncture resistance of at least 12.5 N.

19. A lead-acid battery separator that simultaneously has: a basis weight of at most 130 g / m 2 , a resistance of at most 40 mΩ·cm 2 , and a puncture resistance of at least 12.5 N; wherein, The battery separator comprises a porous membrane and a fiber mat, the porous membrane is laminated to the fiber mat, the porous membrane alone has a residual oil content of ≥10%, and the total residual oil content of the separator is ≤20%.

20. A lead-acid battery separator that simultaneously has a basis weight of up to 130 g / m 2 , a resistance of up to 40 mΩ·cm 2 , and a puncture resistance of at least 12.5 N; wherein, The separator encapsulates the positive or negative electrode, and the bottom edge of the separator is a folded or sealed crease edge, and the side edges are continuous or intermittently sealed seam edges; the battery separator comprises a porous membrane and a fibrous mat, the porous membrane is laminated to the fibrous mat, and at least two opposite edge regions of the porous membrane are not covered by the fibrous mat.

21. A lead-acid battery separator, wherein the serrated protrusions or serrated ribs have an average center distance of 0.1 to 50 mm within a row in the processing direction; adjacent rows of serrated protrusions or serrated ribs are arranged at positions offset in the processing direction; in the offset configuration, adjacent serrated protrusions or serrated ribs are arranged at different positions in the processing direction.

22. A lead-acid battery separator, wherein the negative electrode ribs or back ribs form an angle with the top edge of the separator, and the orientation of the cross ribs is 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15° or 5° relative to the top edge.

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