Improved separator, lead-acid battery, and related method and system

Abstract

To provide an improved lead acid battery separator, which provides reduced ER, reduced separator thickness, increased separator puncture strength, improved separator CMD stiffness, improved separator oxidation resistance, reduced separator basis weight, increased separator hydratability, or a combination thereof, and a lead acid battery.SOLUTION: A lead acid battery separator has a basis weight of approximately 130 g / m2 or less and a bending stiffness in the width direction of approximately 25 mN or more.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] Related Applications This application claims priority to the benefit of International Patent Application No. PCT / US2017 / 023637, filed March 22, 2017.

[0002] In at least selected embodiments, the present disclosure or invention relates to new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same. In at least certain embodiments, the present disclosure relates to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, automotive start light ignition ("SLI") batteries, batteries for idle-start-stop ("ISS") applications, e.g., hybrid-electric vehicles, and / or vehicle batteries such as enhanced flooded batteries ("EFBs"), and / or improved methods of making and / or using such improved separators, cells, batteries, systems, vehicles, and the like. In at least certain embodiments, the disclosure or invention relates to improved separators for enhanced flooded batteries, and / or improved methods of making, testing, and / or using batteries having such improved separators. In at least selected embodiments, the disclosure or invention relates to separators, particularly separators for enhanced flooded batteries having reduced separator electrical resistance ("ER"), reduced separator thickness, increased separator pin puncture strength, improved separator cross-machine direction ("CMD") stiffness, improved oxidation resistance, reduced separator basis weight, increased separator hydration, or combinations thereof. Further disclosed herein are methods, systems, and battery separators that increase battery life, reduce water loss, increase hydration, reduce internal resistance, and / or improve at least the uniformity of enhanced flooded batteries.In at least certain embodiments, the present disclosure or invention relates to an improved separator for enhanced flooded batteries, the separator comprising one or more performance enhancing additives or coatings, reduced electrical resistance, reduced caliper, increased pin puncture strength, improved CMD stiffness, improved oxidation resistance, reduced basis weight, or a combination thereof. [Background technology]

[0003] Enhanced flooded batteries ("EFB") and absorbed glass mat (AGM) batteries have been developed to meet the expanding needs of power sources used in various applications. EFB systems have a similar structure to traditional flooded lead-acid batteries, with positive and / or negative electrodes surrounded by a microporous separator and immersed in a liquid electrolyte. AGM systems, on the other hand, do not contain free liquid electrolyte. Instead, the electrolyte is absorbed into a fiberglass mat layered on top of the electrodes. Historically, AGM systems have been associated with higher discharge power, longer battery life, and better cold cranking current than flooded battery systems. However, AGM batteries are very expensive to manufacture and highly sensitive to overcharging. Therefore, EFB systems remain an attractive option for power sources and storage solutions for portable and stationary applications. Such power sources and storage applications include planar batteries, tubular batteries, vehicle SLI, and hybrid-electric vehicle ISS applications, deep cycle applications, golf car or golf cart and e-rickshaw batteries, batteries operating at partial state of charge ("PSOC"), inverter batteries, and storage batteries for renewable energy resources. and are diverse.

[0004] An EFB system typically includes one or more battery separators inside a lead-acid battery cell that separate the positive electrode from the negative electrode. The battery separator may have two primary functions. First, the battery separator is to keep the positive electrode physically separate from the negative electrode to prevent electrical current from flowing directly between the electrodes (electrical shorting). Second, the battery separator is to allow ionic current flow between the positive and negative electrodes, at least at the ER considered. Battery separators can be made from many different materials, but these two opposing functions are accomplished by battery separators made from porous nonconductors. In this structure, the pores contribute to ionic diffusion between the electrodes, and the nonconductive polymer network prevents electrical shorting.

[0005] Additionally, battery separators other than those mentioned above may be desirable. For example, in addition to reduced electrical resistance (ER), it may be desirable for the separator to have improved pin puncture strength, improved separator cross-machine direction (CMD) stiffness, improved oxidation resistance, reduced separator thickness, and reduced separator basis weight.

[0006] A reduced separator ER can improve battery functionality and increase charge acceptance (reducing time to recharge and / or reducing charging current and / or voltage). If the puncture strength is too low, the separator will puncture at the corners of the lead alloy electrodes during or after assembly, causing shorts and premature battery failure. If the CMD stiffness is too low or too high, it can be difficult to properly handle the separator during battery assembly. Additionally, it may be desirable for battery separators to have improved oxidative stability, thereby extending battery life. A lower basis weight can reduce manufacturing costs. Also, a lower separator thickness may be desirable to reduce the overall size of the battery.

[0007] All of the above features represent a few improvements but may lead to other desirable properties in lead acid batteries, such as increasing the space for more electrolyte, reducing the amount of lead in the electrodes, reducing the size of the battery, and / or reducing the time spent recharging the battery.

[0008] Typical battery separators are microporous to allow ions to pass between the positive and negative electrodes or plates. Separators can be made of polyolefins such as polyethylene and polypropylene, wood, paper, natural or synthetic rubber, PVC or fiberglass. In lead acid batteries such as automotive batteries and / or industrial batteries and / or deep cycle batteries, the battery separator is usually a microporous polyethylene separator, and in some cases such separators may include a backweb and a number of ribs resting on one or both sides of the backweb. See Besenhard, JO, Editor, Handbook of Battery Materials, Wiley-VCH Verlag GmbH, Weinheim, Germany (1999), Chapter 9, pp. 245-292. Some separators for automotive batteries are made in continuous lengths, rolled, and then folded and sealed along the edges (or selected edges) to form a pouch, envelope, sleeve, or pocket that receives the battery's electrodes. For example, certain separators for industrial batteries (or traction batteries or deep cycle batteries) are cut to approximately the same size as the electrode plates (strips or leaves).

[0009] At least for a particular application or battery, a reduction in ER, a reduction in separator thickness, an increase in separator puncture strength, an improvement in separator CMD stiffness, an improvement in separator oxidation resistance, a reduction in separator basis weight, an increase in separator hydration, or a combination thereof. What is needed is an improved separator that provides: More specifically, what is needed is an improved separator and an improved battery including the improved separator that provides increased battery life, reduced battery failure, improved oxidative stability, improved end of charge ("EOC") current, reduced current and / or voltage and / or time required to charge and / or fully charge the battery, minimized internal ER, improved puncture strength, improved separator stiffness, reduced separator thickness, and / or reduced separator basis weight. Exemplary separator embodiments may be used in a variety of lead acid batteries, for example, flooded batteries used in vehicles that use batteries such as EFBs, deep cycle battery applications, SLI batteries for automotive, ISS batteries for hybrid-electric vehicles, and / or inverter batteries. Summary of the Invention

[0010] overview Details of one or more embodiments are set forth below. Other features, objects, and advantages will be apparent from the description and claims. In at least selected embodiments, the disclosure or invention may address the problems or needs described above. In at least certain objects, aspects, or embodiments, the disclosure or invention may provide or disclose new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, methods, and / or vehicles using same. In at least certain embodiments, the present disclosure relates to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, automotive start light ignition ("SLI") batteries, batteries for idle-start-stop ("ISS") applications, hybrid-electric vehicles, and / or vehicle batteries such as enhanced flooded batteries ("EFBs"), and / or improved methods of making and / or using such improved separators, cells, batteries, systems, vehicles, etc. In at least certain embodiments, the present disclosure or invention relates to improved separators for enhanced flooded batteries, and / or improved methods of making, testing and / or using batteries having such improved separators. In at least selected embodiments, the present disclosure or invention relates to separators, particularly separators for enhanced flooded batteries having reduced separator electrical resistance ("ER"), reduced separator thickness, increased separator pin puncture strength, improved separator cross-machine direction ("CMD") stiffness, improved oxidation resistance, reduced separator basis weight, increased separator hydratability, or combinations thereof. Further disclosed herein are methods, systems, and battery separators that increase battery life, reduce water loss, increase hydratability, reduce internal resistance, and / or improve at least enhanced flooded battery uniformity.In at least certain embodiments, the present disclosure or invention relates to an improved separator for enhanced flooded batteries, the separator comprising one or more performance enhancing additives or coatings, reduced electrical resistance, reduced caliper, increased pin puncture strength, improved CMD stiffness, improved oxidation resistance, reduced basis weight, or a combination thereof.

[0011] In at least selected embodiments, the present disclosure or invention may relate to or provide improved separators and / or batteries that overcome the aforementioned problems. For example, the methods, systems and improved battery separators provide reduced ER, reduced separator thickness, increased separator pin puncture strength, improved separator CMD stiffness, improved separator oxidation resistance, reduced separator basis weight, or combinations thereof.

[0012] In selected embodiments of the present invention, about 130 g / m 2 A lead acid battery separator having the following basis weight and a widthwise bending stiffness of about 25 mN or greater can be provided.

[0013] In certain other selected embodiments of the present invention, a lead acid battery separator may be provided having a cross-machine bending stiffness of about 25 mN or less and a backweb thickness of about 125 μm or less.

[0014] In some embodiments of the present invention, the concentration is about 40 mΩ·cm 2 A separator can be provided having a porous membrane having an electrical resistance of about 1.0 N or less, an average puncture resistance of about 11.0 N or more, a 20 hour oxidation resistance of about 200% or more, a 40 hour oxidation resistance of about 100% or more, a backweb thickness of about 125 μm or less, a residual oil amount of about 20% or less, and a residual oil amount of about 10% or more.

[0015] In another aspect of the invention, the lead acid battery separator may have at least one array of ribs, which may have at least one of the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, solid or broken zigzag arranged curved or sinusoidal ribs, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

[0016] In selected embodiments, the separator may have a first array of ribs extending from a first backweb surface having a first rib height measured from the first backweb surface, a second array of ribs extending from a second backweb surface substantially perpendicular to the first array of ribs and having a second rib height measured from the second backweb surface, and may have a base web thickness of about 200 μm or less. The second array of ribs may have a height of about 75 μm or less and a backweb thickness of about 100 μm or less.

[0017] An exemplary separator can have an overall thickness of about 400 μm to about 2.0 mm.

[0018] In certain exemplary embodiments, the lead acid battery separator may have a first array of ribs from the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous or microporous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, curved or sinusoidal ribs arranged in a solid or broken zigzag manner, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

[0019] In other selected embodiments, the lead acid battery separator may have a second array of at least one of the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, curved or sinusoidal ribs arranged in a solid or broken zigzag manner, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

[0020] In selected embodiments, the present invention provides a lead acid battery having a separator substantially as described herein. The battery may be a flat battery, a tubular battery, a flooded lead acid battery, an enhanced flooded lead acid battery, a deep cycle battery, an absorbent glass mat battery, a tubular battery, a lead acid ... The battery may be a power battery, an inverter battery, a vehicle battery, a starting-lighting-ignition ("SLI") battery, an idle-start-stop ("ISS") battery, a car battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid-electric vehicle battery, an electric vehicle battery, an e-rickshaw battery, an e-bike battery, or a marine battery.

[0021] The battery may be operated in a partial state of charge during operation, at rest, or during all of the aforementioned cycles.

[0022] In certain selected embodiments, the present invention provides a vehicle equipped with a lead acid battery having a separator substantially as described herein, the vehicle may be a car, truck, motorcycle, all-terrain vehicle, forklift, golf cart, idle-start-stop vehicle, hybrid-electric vehicle, electric vehicle, e-rickshaw, e-bike, or watercraft.

[0023] Provided are new or improved separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, methods, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, cells, systems, and / or batteries, battery separators having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof, improved separators for enhanced flooded batteries, separators having reduced ER, improved puncture strength, improved separator CMD stiffness, reduced basis weight, or combinations thereof, separators including or exhibiting reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof, and for use in flat batteries, tubular batteries, SLI and HEV for vehicles. ISS applications, deep cycle applications, golf cars or golf carts, and e-rickshaw batteries, batteries operating at partial state of charge ("PSOC"), inverter batteries, storage batteries for renewable energy resources and combinations thereof, and / or as shown, claimed or described herein.

[0024] In at least selected embodiments, the present disclosure or invention relates to new or improved separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, methods, and / or vehicles using same. In at least certain embodiments, the present disclosure relates to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, automotive start light ignition ("SLI") batteries, batteries for idle-start-stop ("ISS") applications, e.g., hybrid-electric vehicles, and / or vehicle batteries such as enhanced flooded batteries ("EFBs"), and / or improved methods of making and / or using such improved separators, cells, batteries, systems, vehicles, and the like. In at least certain embodiments, the present disclosure or invention relates to improved separators for enhanced flooded batteries, and / or improved methods of making, testing, and / or using batteries having such improved separators. In at least selected embodiments, the present disclosure or invention relates to improved separators for enhanced flooded batteries, particularly batteries having reduced separator electrical resistance ("ER"), reduced separator thickness, increased separator puncture strength, improved separator cross-machine direction ("CMD") stiffness, improved oxidation resistance, reduced separator basis weight, increased separator hydration, or a combination thereof. Further disclosed herein are methods, systems and battery separators that increase battery life, reduce water loss, increase hydration, reduce internal resistance, and / or improve uniformity of at least an enhanced flooded battery. In at least certain embodiments, the disclosure or invention relates to improved separators for enhanced flooded batteries, the separators comprising one or more performance enhancing additives or coatings, reduced electrical resistance, reduced caliper, increased pin puncture strength, improved CMD stiffness, improved oxidation resistance, reduced basis weight, or combinations thereof.

[0025] In at least selected embodiments, the present disclosure relates to improved lead acid batteries, e.g., flooded lead acid batteries, improved systems including lead acid batteries and / or battery separators, improved battery separators, improved vehicles including such systems, methods of manufacture, testing or use, or combinations thereof. In at least certain embodiments, the present disclosure or invention relates to improved flooded lead acid batteries, improved battery separators for such batteries, and / or methods of manufacture, testing or use of such improved flooded lead acid batteries, or combinations thereof. Further disclosed herein are methods, systems, batteries and / or battery separators that reduce electrical resistance, reduce separator thickness, increase separator puncture strength, improve separator CMD stiffness, improve separator oxidation resistance, reduce separator basis weight, increase separator hydration, or combinations thereof. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a schematic diagram of an exemplary lead acid battery. [Diagram 2] 1 is a schematic diagram of two exemplary surfaces of a separator of the present invention. [Figure 3A] 3A-3C illustrate an embodiment of an exemplary separator and various major dimensions thereof: Fig. 3A is a schematic diagram of a positive electrode facing surface of an exemplary separator. [Figure 3B]FIG. 3B is a cross-sectional view (indicated by AA in FIG. 3A) of an exemplary separator shown along the longitudinal direction. [Figure 3C] FIG. 3B is a cross-sectional view of an exemplary separator shown along the width direction (indicated by bb in FIG. 3B). [Figure 4] 1 illustrates different embodiments of a separator having exemplary rib features. [Diagram 5] 1 illustrates the tip used to puncture the test separator. [Figure 6] 1 is a schematic rendering of a separator bending test. [Figure 7A] 1 is a schematic rendering of a sample for elongation testing. [Figure 7B] 1 illustrates the sample holder for elongation testing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Detailed Description The embodiments described herein can be more readily understood by reference to the following detailed description, examples, and figures. Among other things, various batteries, vehicles or devices, and methods for preventing acid stratification are described herein, but this is not limited to the specific embodiments shown in the detailed description, examples, and figures. It should be recognized that these embodiments are merely illustrative of the principles of the invention. Several modifications and applications will be readily apparent to those skilled in the art without departing from the disclosed subject matter.

[0028] lead acid battery 1, an exemplary flooded lead-acid battery 50, such as an EFB, includes an array 50a of alternating positive and negative electrodes 52, 54, where the positive and negative electrodes 52, 54 are interleaved with one another. The array 50a further includes a separator 100 interleaved between each electrode 52, 54, which separates the electrodes 52, 54 and prevents contact between the electrodes 52, 54. The array 50a includes a sulfuric acid (H2SO4) electrolyte 56 (e.g., about 1 The positive electrode 52 is in electrical communication with the positive terminal 51 and the negative electrode 54 is in electrical communication with the negative terminal 53.

[0029] Referring to FIG. 2, the separator 100 includes a porous membrane and further includes one or more arrays of ribs extending from the porous membrane 102 on one or both sides of its surface. The porous membrane 102 includes a positive electrode-facing surface 102p, since this surface faces the positive electrode when the separator is placed in a lead-acid battery, and a negative electrode-facing surface 102n, since this surface faces the negative electrode when the separator is placed in a lead-acid battery. The positive ribs 104 can extend from the positive electrode-facing surface 102p, and the negative ribs 106 can extend from the negative electrode-facing surface 102n. The separator further includes a length direction and a width direction, as delineated by the arrows indicated by the length direction md and the width direction cmd, the two directions being substantially perpendicular to each other. An exemplary separator can have the positive ribs 104 extending substantially in the length direction md and the negative ribs 106 extending substantially in the width direction cmd. Referring back to FIG. 1, the machine direction md of the exemplary separator 100 runs substantially between the top and bottom of the cell 50, and the cross direction cmd is substantially perpendicular to the machine direction md.

[0030] Additionally, the exemplary separator 100 may be coupled to, adjacent to, or laminated to one or more fiber mats (not shown).

[0031] The lead acid batteries described herein are not limited to, and may be flooded lead acid batteries, such as enhanced flooded lead acid batteries, absorbent glass mat ("AGM") batteries, valve regulated lead acid batteries ("VRLA") batteries, gel batteries, etc. In some preferred embodiments, the lead acid batteries described herein are flooded lead acid batteries, as at least some of the disclosures herein are directed to solving the problems of flooded lead acid batteries, particularly flooded lead acid batteries operating at or within a partial state of charge, namely acid stratification and active material shedding.

[0032] As described herein, the exemplary separators can be used in lead-acid batteries for various applications. Such applications can include, for example, partial state of charge applications, deep cycle applications, motor vehicle applications, truck applications, motorcycle applications, fork trucks, golf carts (also called golf cars), electric vehicle applications, hybrid-electric vehicle ("HEV") applications, ISS vehicle applications, e-rickshaw applications, e-trike applications, e-bike applications, boat applications, renewable and / or alternative energy collection and storage applications, such as wind energy, solar energy, and the like. Furthermore, the exemplary separators can be used in various batteries. Such batteries may include, for example, flooded lead acid batteries, such as enhanced flooded lead acid batteries, AGM batteries, VRLA batteries, plate batteries, tubular batteries, partial state of charge batteries, deep cycle batteries, automobile batteries, truck batteries, motorcycle batteries, fork truck batteries, motocycle batteries such as golf carts (also called golf cars), electric vehicle batteries, hybrid-electric vehicle ("HEV") batteries, ISS vehicle batteries, e-rickshaw batteries, e-trike batteries, e-bike batteries, boat batteries, energy collection and storage, e.g., collection and storage of renewable and / or alternative energy such as wind energy, solar energy, and the like, and the like.

[0033] Separator The separator 100 must prevent electrical conductivity of the electrodes 52, 54 but allow ionic conductivity of the electrodes 52, 54. Thus, exemplary embodiments of the separator 100 of the present invention include microporous membranes having pores less than about 5 μm, preferably less than about 1.0 μm, mesoporous membranes, or macroporous membranes having pores greater than about 1.0 μm. In a preferred embodiment, the exemplary porous membrane is a microporous membrane having a pore size of about 0.1 μm and a porosity of about 60% to about 68%.

[0034] The porous membrane is not so limited, but may be any porous membrane, porous membrane with any pore size (e.g., macroporous, microporous, nanoporous, etc.), and made from a material that is 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 may be a polyethylene battery separator manufactured or to be manufactured by Daramic® or other manufacturers of lead acid battery separators.

[0035] In some embodiments, the pore size 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 less. Preferably, at least 90% of the pores have a diameter of less than 0.9 μm. The microporous separator preferably has an average pore size of 0.05 μm to 0.9 μm, for example, 0.1 μm to 0.3 μm.

[0036] physical properties 3A-3C, the exemplary separator 100 has a top edge 101, a bottom edge 103, side edges 105a, 105b, a machine direction ("MD") and a cross-machine direction ("CMD"). The exemplary separator 100 can include a series of primary or positive ribs 104 extending from a porous membrane backweb 102, a positive electrode facing surface 102p. As shown, the ribs 104 are segmented or serrated. However, the ribs 104 can also be ribs, grooves, textured areas, serrated or crenellated ribs, solid ribs, battlemented or battlemented ribs, broken ribs, angled ribs, linear ribs, curved or sinusoidal ribs, zigzag ribs, embossed patterns, dimples, and / or ribs extending on or from the backweb 102, or combinations thereof. The exemplary embodiment places the separator 102 in the cell (not shown) with the ribs 104 facing the positive electrode (not shown), although this is not critical. If the ribs 104 face the positive electrode, the ribs may be known as positive ribs. Backweb Detail the longitudinal direction md, the height of the positive rib Height Pos , Height of negative rib NegThe separator 100 is shown with the combination of the separator 100 and the total separator thickness Overall FIG. 3B shows the backweb thickness Backweb and negative rib height Neg The sum of the base web thickness Baseweb FIG. 3C shows separator 100 widthwise showing negative ribs 106 disposed laterally in the widthwise direction (hereafter discussed and further indicated as "negative cross ribs" or "NCR"). FIG. 3C further shows positive rib serrations 104s. Separator 100 is typically placed in a cell that positions the negative cross ribs toward the negative electrode, although this is not critical. Even without the negative cross ribs, the backweb thickness Thickness Backweb is the base web thickness Baseweb It will be understood that Figures 3A-3C are not to scale.

[0037] rib In certain selected aspects of the invention, either or both of the positive and / or negative ribs may be solid ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, solid or broken zigzag arranged curved or sinusoidal ribs, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs and / or combinations thereof.

[0038] In various possible preferred embodiments, the porous membrane 102 may have ribs 104, 106, which may be positive ribs or negative cross ribs located on either surface of the membrane 102. The ribs 104, 106 may be ribs, grooves, textured areas, serrated or crenulated ribs, solid ribs, battlemented or battlemented ribs, broken ribs, angled ribs, linear ribs, curved or sinusoidal ribs, zigzag ribs, embossed patterns, dimples, and / or ribs extending to or from the backweb, or combinations thereof. In some embodiments, the ribs may be present on only one of the surfaces of the porous membrane, or on both sides of the membrane. The separator may include positive ribs on the first side or first surface, positive side or surface, or front side or front surface of the porous membrane, and negative cross ribs on the second side, negative side or rear of the separator. Such negative cross ribs may be smaller and more closely spaced than the positive ribs. The positive rib 104 has a height of 8 μm to 1 mm. Pos and may be spaced apart from 1 μm to 20 mm, and the preferred backweb thickness of the microporous polyolefin porous membrane (not including ribs or embossed features) Backweb can be from about 50 μm to about 500 μm (e.g., in certain embodiments, about 125 μm or less). For example, the ribs can be spaced apart 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, as well as in increments up to 20 mm.

[0039] The NCR 106 has a height of about 25 μm to about 100 μm, preferably about 50 μm to 75 μm. Neg For example, the NCR 106 may be about 25 μm to about 250 μm, preferably about 50 μm to 125 μm, or preferably about 50 μm to 75 μm.

[0040] In some embodiments, the positive ribs 104 may be on a first surface of the porous membrane 102 and the negative or negative cross ribs 106 may be on a second surface of the porous membrane substantially at 90° to the positive ribs 104. In some embodiments, the positive ribs 104 may be on a first surface of the porous membrane 102 and may be generally disposed perpendicular to the top end 101 of the separator 100 and the negative or negative cross ribs 106 may be on a second surface of the porous membrane 102 and may be generally disposed parallel to the top end 101 of the separator 100. In some embodiments, the positive ribs 104 may be on a first surface of the porous membrane and may be generally disposed parallel to the machine direction md of the separator 100 and the negative or negative cross ribs 106 may be on a second surface of the porous membrane 102 and may be generally disposed parallel to the width direction cmd of the separator. In some embodiments, the positive ribs 104 may be on a first surface of the porous membrane and may be disposed at an angle of about 0° to about 180° or about 180° to about 360° with respect to the machine direction md of the separator 100, and the negative or negative cross ribs 106 may be on a second surface of the porous membrane and may be disposed generally parallel to the top edge 101 or width direction cmd of the separator 100. In some embodiments, the positive ribs 104 may be on a first surface of the porous membrane and the negative mini-ribs 106 may be on a second surface of the porous membrane 102 and may be disposed generally parallel to the positive ribs 104 on the first surface of the porous membrane.

[0041] The ribs may be serrated in certain embodiments. The serrated or serrated ribs may have an average tip length of about 0.05 mm to about 1 mm. For example, the average tip length may be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0042] The serrations or sawtooth ribs may have an average base length of about 0.05 mm to about 1 mm. For example, the average base length 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.

[0043] When serrations or serrated ribs are present, the ribs may have an average height of about 0.05 mm to about 4 mm. For example, the average height may be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less. For embodiments in which the height of the serrations is the same as the height of the ribs, the serrated ribs may also be referred to as protrusions. Such ranges may apply to separators in industrial traction start / stop batteries, where the total separator thickness may typically be from about 1 mm to about 4 mm, similar to automotive start / stop batteries, although the total separator thickness may be slightly less (typically from about 0.3 mm to about 1 mm).

[0044] The serrations or serrated ribs may have a center-to-center pitch within a longitudinal column of about 0.1 mm to about 50 mm. For example, the average center-to-center pitch may be greater than or equal to about 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 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 columns of serrations or serrated ribs may be equally positioned at the same longitudinal or offset location. In an offset configuration, adjacent serrations or serrated ribs are positioned at different longitudinal locations. FIG. 3A shows serrated ribs positioned in an offset configuration.

[0045] The serrations or serrated ribs can have an average height to base width ratio of about 0.1:1 to about 500:1. For example, the average height to base width ratio can be 0.1:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, or 450:1 or more, and / or can be 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, or 25:1 or less.

[0046] The serrations or serrated ribs can have an average base width to tip width ratio of about 1000:1 to about 0.1:1. For example, the average base width to tip width ratio can be 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 or more. and / or may be less than 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.

[0047] In some embodiments, the separator may feature ribs, sawtooth or serrated ribs, dimples, or combinations thereof. For example, the separator may have a series of sawtooth ribs that are continuous from top to bottom along the separator, and a series of sawtooth ribs that are continuous horizontally along the separator. In other embodiments, the separator may feature sawtooth ribs, dimples, continuous, interrupted or broken solid ribs, or combinations thereof. It is possible.

[0048] In some selected embodiments, the porous separator may have negative longitudinal or cross ribs on the opposite side of the membrane as protrusions. The negative or back ribs may be parallel to the top edge of the separator or may be disposed at an angle thereto. For example, the cross ribs may be oriented at an angle of about 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15°, or 5° relative to the top edge. The cross ribs may be oriented at an angle of about 90°-60°, 60°-30°, 60°-45°, 45°-30°, or 30°-0° relative to the top edge. Typically, the cross ribs are present on the side of the membrane that faces the negative electrode. In some embodiments of the invention, the ribbed membrane has a transverse cross rib height of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. Neg In some embodiments of the invention, the membrane over the ribs may have a transverse cross rib height of about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm or less.

[0049] In some embodiments of the invention, the ribbed membrane may have a transverse cross rib width of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the invention, the ribbed membrane may have a transverse cross rib width of no more than about 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0050] In some selected embodiments, the porous membrane can have a transverse cross rib height of about 0.10-0.15 mm and a longitudinal rib height of about 0.10-0.15 mm. In some embodiments, the porous membrane can have a transverse cross rib height of about 0.10-0.125 mm and a longitudinal rib height of about 0.10-0.125 mm.

[0051] Thickness In certain selected embodiments, the exemplary microporous membrane has a backweb thickness that can be 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. Backweb The ribbed separator may have a backweb thickness of 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 up to 50 μm. In some embodiments, the microporous membrane may have a backweb thickness of 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 backweb thickness of about 125 μm or 200 μm.

[0052] In certain selected embodiments, exemplary separators have a total thickness of at least about 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, or more, and up to about 1.0 mm to about 2.0 mm or more. Overall may have:

[0053] Basis weight In certain selected embodiments, the exemplary separator may be characterized by its basis weight (also referred to as area weight) measured in units of g / m2. The exemplary separator may exhibit a reduced basis weight. For example, the exemplary separator may have a basis weight of 140 g / m2. 2 Below 130g / m 2 Below 120g / m 2 Below 110g / m 2 Below 100g / m 2 Below 90g / m 2 An exemplary separator may have a basis weight of about 130 g / m 2 ~about 90g / m 2 or less, and preferably about 120 g / m 2 It may have a basis weight of about 90 g / m2 or less.

[0054] Basis weight is simply measured by weighing a sample and then dividing by the area of ​​the sample. For example, take 1.0m of a 1.0m sample and weigh it. The area is calculated without taking into account ribs, grooves, embossing etc. For example, 1.0m of a 1.0m sample of ribbed separator has the same area as 1.0m of a 1.0m sample of flat separator.

[0055] envelope The separator 100 may be provided as a flat sheet, a leaf, a wrap, a sleeve, or an envelope or pocket separator. An exemplary envelope separator may encase a positive electrode (a "positive-encasing separator"), with the separator having two insides facing the positive electrode and two outsides facing the adjacent negative electrode. Alternatively, another exemplary envelope separator may encase a negative electrode (a "negative-encasing separator"), with the separator having two insides facing the negative electrode and two outsides facing the adjacent positive electrode. In such an envelope separator, the bottom end 103 may be a folded or sealed creased end. Additionally, the lateral ends 105a, 105b may be continuously or intermittently sealed seam ends. The ends may be bonded or sealed by adhesive, heat, ultrasonic welding, or the like, or a combination thereof.

[0056] Some other exemplary embodiments of separator assembly configurations include ribs 104 facing the positive electrode, ribs 104 facing the negative electrode, negative or positive electrode envelopes, negative or positive electrode sleeves, negative or positive electrode hybrid envelopes, both electrodes may be wrapped or sleeved, and combinations thereof. For example, Figures 4A-4C depict several embodiments of ribbed separators (such as strips, sleeves, envelopes, or pockets) with different rib profiles. The ribs shown are positive ribs on the negative plate envelope (the negative plate is inside the envelope). The angled rib pattern of Figure 4A may possibly be preferred to the Daramic® RipTide™ acid blend rib profile, which may help to remove or eliminate acid stratification in certain batteries. The profile of Figure 4B may be a longitudinal sawtooth rib pattern. The profile of Figure 4C may be a diagonal offset rib pattern. The negative surface has no ribs (smooth), same ribs, smaller ribs, longitudinal mini-ribs, cross mini-ribs or NCR, diagonal ribs or combinations thereof.

[0057] Certain exemplary separators can be processed to form hybrid envelopes. Hybrid envelopes can be provided by folding a sheet of separator in half and joining the separator sheet edges together to form one or more slits or apertures before, during, or after forming the envelope. The length of the apertures can be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the length of the entire edge. The length of the apertures can be at least 1 / 50-1 / 3, 1 / 25-1 / 3, 1 / 20-1 / 3, 1 / 20-1 / 4, 1 / 15-1 / 4, 1 / 15-1 / 5, or 1 / 10-1 / 5 of the length of the entire edge. Hybrid envelopes can have 1-5, 1-4, 2-4, 2-3, or 2 apertures, which may or may not be evenly spaced along the length of the bottom edge. It is preferred that the corners of the envelope are free of openings. The slits may be cut after the separator is folded and sealed into the envelope, or the slits may be formed prior to forming the porous membrane into the envelope.

[0058] Combination with fiber mats In certain embodiments, the exemplary porous membrane may be further laminated to another layer, such as a fiber mat, that enhances wicking properties and / or enhances electrolyte wetting or retention properties. The mat may be woven or non-woven, glass or synthetic, single layer, multi-layer (each layer may have the same, similar or different characteristics as the other layers), or combinations thereof.

[0059] When a fibrous layer is present, the microporous membrane preferably 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. It is preferred that at least two opposite end regions of the membrane layer remain uncovered, providing heat sealing at the edges to facilitate optional formation of pockets or envelopes. Such a fibrous mat may have a thickness of at least 100 μm, 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, etc. The subsequently laminated separator may be cut into several pieces. In a particular embodiment, the fibrous mat is laminated to the ribbed surface of the microporous membrane. In certain embodiments, the separator can be supplied in rolls and / or cut pieces, thus providing battery manufacturers with handling and / or assembly advantages with the improved separators described herein. As previously mentioned, the improved separators can be stand-alone separator sheets or layers without the addition of one or more fiber mats or the like.

[0060] composition The porous membranes may be made from natural or synthetic substrates, engineered plasticizers, and fillers, and optionally other additives and / or coatings, and the like.

[0061] Base material In certain embodiments, exemplary natural or synthetic substrates may include polymers, thermoplastic polymers, phenolic resins, natural or synthetic rubbers, synthetic wood pulp, glass fibers, synthetic fibers, cellulosic fibers, and combinations thereof. In certain preferred embodiments, the exemplary separator may be a microporous membrane made from a thermoplastic polymer. Exemplary thermoplastic polymers may essentially include any acid-resistant thermoplastic material suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers may include polyvinyls and polyolefins. In certain embodiments, polyvinyls may include, for example, polyvinyl chloride ("PVC"). In certain preferred embodiments, polyolefins may include, for example, polyethylene, polypropylene, ethylene-butene copolymers, and combinations thereof, with polyethylene being preferred. In certain embodiments, exemplary natural or synthetic rubbers may include, for example, latex, non-crosslinked or crosslinked rubber, crumb rubber or ground rubber, and combinations thereof.

[0062] In certain embodiments, the layers of the porous membrane preferably comprise a polyolefin, particularly polyethylene. Preferably, the polyethylene is a high molecular weight polyethylene ("HMWPE") (e.g., a polyethylene having a molecular weight of at least 600,000). More preferably, the polyethylene is an ultra-high molecular weight polyethylene ("UHMWPE") (e.g., a polyethylene having a molecular weight of at least 1,000,000, particularly greater than 4,000,000, and most preferably from 5,000,000 to 8,000,000, as measured by viscometry and calculated according to the Margolie equation), a standard load melt index of substantially zero (0) (as measured as directed in ASTM D 1238 (Condition E) using a standard load of 2,160 g), and a viscosity number of less than 600 ml / g, preferably less than 1,000 ml / g, more preferably less than 2,000 ml / g, and most preferably less than 3,000 ml / g (as measured on a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C).

[0063] Plasticizer In certain embodiments, exemplary processing plasticizers may include process oils, petroleum-based oils, paraffinic mineral oils, mineral oils, and combinations thereof.

[0064] In some embodiments, the separator has a total residual or final oil content of about 0.5% to about 40% by weight, and in some embodiments, about 10% to about 30% residual processing oil, and in some examples, about 20% to about 30% residual processing oil or residual oil, by weight of the separator sheet product. In some exemplary embodiments, the porous membrane alone can have a residual oil content of about 10% or less, and the separator (porous membrane and ribs) can have a residual oil content of about 20% or less.

[0065] Filler In certain embodiments, exemplary fillers may include dry fine silica, precipitated silica, amorphous silica, alumina, talc, fish meal, fish bone meal, and the like, and combinations thereof. In certain preferred embodiments, the filler is one or more of silica, fumed silica, precipitated silica, friable silica, dispersed silica, and the like. Silica, having a relatively high level of oil absorption and a relatively high level of affinity for plasticizers (e.g., mineral oil), is desirably dispersed in a mixture of polyolefin substrate (e.g., polyethylene) and mineral oil when forming lead acid battery separators of the type set forth herein. In some selected embodiments, the filler has an average particle size of 25 μm or less, and in some examples 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm or less. In some examples, the average particle size of the silica filler particles is between 15 μm and 25 μm. The particle size of the silica filler and / or the surface area of ​​the silica filler contribute to the absorption of oil. The final silica particles or separator may be within the size ranges described above. However, the initial silica used as raw material may be one or more agglomerates and / or aggregates, having a size of about 200 μm or greater.

[0066] The filler may further reduce the so-called hydration layer of electrolyte ions, enhancing their passage through the membrane, thereby again decreasing the total electrical resistance or ER of the battery, such as an enhanced flooded battery or system.

[0067] The filler contains various species (e.g., polar species such as metals) that facilitate the flow of electrolytes and ions in the separator, which also reduces the overall electrical resistance so that the separator can be used in flooded batteries, such as enhanced flooded batteries.

[0068] Additives / Surfactants In certain embodiments, the exemplary separator may include one or more performance enhancing additives added to the separator or porous membrane. The performance enhancing additives may be surfactants, wetting agents, colorants, antistatic agents, antimony suppression additives, UV protection additives, antioxidants, and the like, and combinations thereof. In certain embodiments, the additive surfactants may be ionic, cationic, anionic, or nonionic surfactants.

[0069] In certain embodiments described herein, small amounts of anionic or nonionic surfactants are added to the porous membranes or separators of the present invention. Desirable properties of small amounts of surfactants may include low total organic carbon ("TOC") and / or low volatile organic compounds ("VOC").

[0070] Certain suitable surfactants are nonionic, while other suitable surfactants are anionic. The additive may be a single surfactant, a mixture of two or more surfactants, for example, two or more anionic surfactants, two or more nonionic surfactants, or a mixture of at least two or more anionic surfactants. The surfactant may be at least one ionic surfactant and at least one nonionic surfactant. Certain suitable surfactants may have an HLB value of less than 6, preferably less than 3. The use of these certain suitable surfactants in conjunction with the separator of the present invention described herein may further improve the separator when used in a lead acid battery, reduce water loss, reduce antimony poisoning, improve cycling, reduce float current, reduce float potential, or combinations thereof. Suitable surfactants include surfactants such as salts of alkyl sulfates, alkylarylsulfonates, alkylphenol-alkylene oxide addition products, soaps, alkyl-naphthalene-sulfonates, one or more sulfosuccinates such as anionic sulfosuccinates, dialkyl esters of sulfosuccinates, amino compounds (primary, secondary, tertiary or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, and mono- and dialkyl phosphate esters. Additives may include non-ionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicon surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters and sucrose esters of fatty acids.

[0071] In certain embodiments, the additive may be represented by a compound of formula (I).

[0072] [ka]

[0073] R is a linear or non-aromatic hydrocarbon radical having 10 to 4200, preferably 13 to 4200, carbon atoms, which may be interrupted by oxygen atoms. When k=1 or 2,

[0074] [ka]

[0075] or

[0076] [ka]

[0077] Preferably, H. M is an alkali metal or alkaline earth metal ion, H + or NH4 + and all variables M have the meaning H + Not having n=0 or 1, m=0 or an integer from 10 to 200; x=1 or 2.

[0078] The ratio of oxygen atoms to carbon atoms in the compounds of formula (I) is from 1:1.5 to 1:30, and m and n cannot simultaneously be 0. However, preferably, exactly one of the variables n and m is different from 0.

[0079] A non-aromatic hydrocarbon radical means a radical that does not contain an aromatic group or that itself represents one non-aromatic hydrocarbon radical, which may be interrupted by an oxygen atom (i.e., it contains one or more ether groups).

[0080] R is preferably a straight-chain or branched aliphatic hydrocarbon radical, which may be interrupted by oxygen atoms. Saturated, non-bridged hydrocarbon radicals are particularly preferred. However, as noted above, R may, in certain embodiments, include an aromatic ring.

[0081] For the manufacture of battery separators, the compounds of formula (I) can be used to provide effective protection against oxidative degradation.

[0082] Preferred is a battery separator comprising a compound of formula (I) R is a hydrocarbon group having 10 to 180, preferably 12 to 75, particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20, particularly preferably 1 to 8 oxygen atoms, particularly preferably the group represented by the formula

[0083] [ka]

[0084] is a hydrocarbon radical of R 2 is an alkyl radical having 10 to 30 carbon atoms, preferably having 12 to 25, particularly preferably having 14 to 20 carbon atoms, R 2 may be linear or non-linear, including aromatic rings; P is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4; q is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4; Particularly preferred are compounds in which the sum of p and q is 0 to 10, particularly 0 to 4. n=1, m=0.

[0085] formula

[0086] [ka]

[0087] is understood to include compounds in which the arrangement of the bracketed groups differs from that shown. For example, compounds of the invention in which the bracketed radicals are formed by alternating (OC2H4) and (OC3H6) groups are suitable.

[0088] R 2 Linear or branched alkyl radicals having 10 to 20, preferably 14 to 18, carbon atoms have proven to be particularly advantageous. OC2H4 is preferably an abbreviation for OCH2CH2 and OC3H6 is an abbreviation for OCH(CH3)2 and / or OCH2CH2CH3.

[0089] As preferred additives, in the particular alcohols, (p=q=0; m=0) primary alcohols are particularly preferred, with fatty alcohol ethoxylates (p=1-4, q=0), fatty alcohol propylene oxides (p=0; q=1-4) and fatty alcohol alkoxylates (p=1-2; q=1-4) of primary alcohols being preferred. Fatty alcohol alkoxylates are, for example, ethylene oxide or propylene oxide-containing ethoxylates. It can be accessed by reaction of the corresponding alcohols.

[0090] Additives of type m=0 are not or are difficult to dissolve in water, and sulfuric acid has proven to be particularly advantageous.

[0091] Also preferred is an additive comprising a compound of formula (I) R is an alkane radical having 20 to 4200, preferably 50 to 750 and particularly preferably 80 to 225 carbon atoms, M is an alkali metal or alkaline earth metal ion, H + or NH4 + In particular, Li +、 Na + and K + Or H + In alkali metal ions such as + Not having n=0, m = an integer between 10 and 200; x=1 or 2.

[0092] Salt Additives In a particular embodiment, suitable additives may include, in particular, polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers, in which the acid groups are at least partially neutralized, preferably 40%, particularly preferably 80%. This percentage refers to the number of acid groups. Particularly preferred is poly(meth)acrylic acid, which is entirely present in salt form. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn and ammonium (NR4, where R is either hydrogen or a carbon functional group). Poly(meth)acrylic acid may include polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acid is preferred, in particular polyacrylic acid with an average molar mass Mw of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, and particularly preferably 1,000 to 4,000 g / mol. The molecular weight of poly(meth)acrylic acid polymers and copolymers is determined by measuring the viscosity of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution (Fikentscher constant).

[0093] Copolymers of (meth)acrylic acid are also suitable, in particular those which, in addition to (meth)acrylic acid, comprise ethylene, maleic acid, methyl acrylate, butyl acrylate and / or ethylhexyl acrylate as comonomers. Preference is given to copolymers which comprise at least 40% by weight and in particular at least 80% by weight of (meth)acrylic acid monomer, the proportion being based on the acid form of the monomer or polymer.

[0094] Alkali metal and alkaline earth metal hydroxides, such as potassium hydroxide and especially sodium hydroxide, are particularly suitable for neutralizing polyacrylic acid polymers and copolymers. Additionally, coatings and / or additives that strengthen the separator may include, for example, metal alkoxides, where the metals may include, by way of example only (and not intended to be limiting), Zn, Na, or Al, by way of example only, sodium ethoxide.

[0095] In some embodiments, the microporous polyolefin porous membrane may include a coating on one or both sides of such layer. Such coating may include surfactants or other materials. In some embodiments, the coating may include one or more materials described, for example, in U.S. Patent Application Publication No. 2012 / 0094183, incorporated herein by reference. Such coating may, for example, reduce the overcharge voltage of the battery system, thereby extending the battery life with less grid corrosion, and preventing drying and / or moisture loss.

[0096] ratio In certain selected embodiments, the membrane may be prepared by combining, by weight, about 5-15% polymer, in some instances about 10% polymer, about 10-75% filler, in some instances about 30% filler, about 10-85% process oil, and in some instances about 60% process oil. In other embodiments, the filler content is reduced and the oil content is increased to about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or greater than 70% by weight. The filler:polymer ratio (by weight) may be about 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 (or may be between about these specified ranges). The ratio of filler:polymer (by weight) can be from about 1.5:1 to about 6:1, in some examples from 2:1 to 6:1, from about 2:1 to 5:1, from about 2:1 to 4:1, and in some examples from about 2:1 to about 3:1. The amounts of filler, oil, and polymer (e.g., polyethylene) are all balanced for the desired separator properties, such as runnability and electrical resistance, basis weight, puncture resistance, flexural stiffness, oxidation resistance, porosity, drop strength, flexural strength, and the like.

[0097] In at least one embodiment, the microporous membrane can include UHMWPE mixed with processing oil and precipitated silica. In 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 agents common to the separator art (e.g., surfactants, wetting agents, colorants, antistatic agents, antioxidants, etc., and combinations thereof). In a particular example, the microporous polymer layer can be a homogeneous mixture of 8-100% by volume polyolefin, 0-40% by volume plasticizer, and 0-92% by volume inert filler. A preferred plasticizer is a petroleum-based oil. Plasticizers are useful for imparting porosity to battery separators because they are the easiest component to remove from a polymer-filler-plasticizer composition.

[0098] Microporous membranes made according to the present invention include polyethylene and a filler (e.g., silica), and typically have a residual oil content, which in some embodiments is about 0.5% up to about 40% of the total weight of the separator membrane (in some examples, about 10-40% of the total weight of the separator membrane, and in some examples, about 20-40% of the total weight). In certain selected embodiments herein, the residual oil content of the separator can be replaced by adding more of a performance enhancing additive, such as a surfactant having a hydrophilic lipophilic balance ("HLB") of less than 6, or a non-ionic surfactant. For example, the performance enhancing additive, such as a surfactant, non-ionic surfactant, can comprise up to 0.5% of the total weight of the microporous separator membrane, up to the total amount of the residual oil (e.g., up to 20%, 30% or even 40%), thereby partially or completely replacing the residual oil of the separator membrane.

[0099] manufacturing In some embodiments, the exemplary porous membrane can be made by mixing the components in an extruder. For example, about 30% by weight silica with about 10% by weight UHMWPE and about 60% processing oil can be mixed in an extruder. The exemplary microporous membrane can be made by passing the components through a hot press and passing the extrudate produced by the extruder through a die and into a nip formed by two heating steps, a calender stack or rolls to form a continuous web. The calender rolls also establish a base web thickness TBASE and / or a back web thickness TBACK. A substantial amount of the processing oil from the web can be extracted using a solvent. The web can be dried and slit into lanes of a predetermined width and then wound into a roll. Alternatively or additionally, the press or calendar rolls can be engraved with various groove patterns to provide ribs, grooves, textured areas, serrated or crenellated ribs, battlemented or battlemented ribs, fractured ribs, angled ribs, linear ribs, or curved or sinusoidal ribs, embossing, dimples, and the like, which extend into the microporous membrane or combinations thereof, or thence into the separator.

[0100] Surfactant-based production In certain selected embodiments, optional additives or agents (e.g., surfactants, wetting agents, colorants, antistatic agents, antioxidants, and the like, and combinations thereof) may also be mixed in the extruder along with other components. The microporous membranes described herein may be extruded into a sheet or web shape and finished substantially as described above.

[0101] In certain embodiments, when added or alternately added to the extruder, the additive is applied to the separator porous membrane, for example, when it is finished (e.g., after extracting much of the process oil). According to certain preferred embodiments, the additive or a solution of the additive (e.g., an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for the application of non-thermally stable additives and additives that are soluble in the solvent used to extract the process oil. Particularly suitable as 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 additive can be applied to the side facing the negative electrode, the side facing the positive electrode, or to both sides of the separator. The additive can also be applied in a solvent bath during the extraction of the pore former (e.g., process oil). In certain selected embodiments, some of the performance enhancing additives, such as surfactant coatings, or performance enhancing additives added to the extruder prior to making the separator (or both) may combine with, inactivate and / or form compounds with the antimony in the battery system and / or may drop to the mud rest of the battery and / or prevent it from precipitating on the negative electrode.

[0102] In certain embodiments, the additive (e.g., a nonionic surfactant, an anionic surfactant, or a mixture thereof) is present in an amount of at least 0.5 g / m 2 , 1.0g / m 2 , 1.5g / m 2 , 2.0g / m 2 , 2.5g / m 2 , 3.0g / m 2 , 3.5g / m 2 , 4.0g / m 2 , 4.5g / m 2 , 5.0g / m 2 , 5.5g / m 2 , 6.0g / m 2 , 6.5g / m 2 , 7.0g / m 2 , 7.5g / m 2 , 8.0g / m 2 , 8.5g / m 2 , 9.0g / m 2, 9.5g / m 2 , 10.0g / m 2 or up to about 20.0 g / m 2 The additives may be present at a density or add-on level of 0.5 to 15 g / m 2 , 0.5~10g / m 2 , 1.0~10.0g / m 2 , 1.5~10.0g / m 2 , 2.0~10.0g / m 2 , 2.5~10.0g / m 2 , 3.0~10.0g / m 2 , 3.5~10.0g / m 2 , 4.0~10.0g / m 2 , 4.5~10.0g / m 2 , 5.0~10.0g / m 2 , 5.5~10.0g / m 2 , 6.0~10.0g / m 2 , 6.5~10.0g / m 2 , 7.0~10.0g / m 2 , 7.5~10.0g / m 2 , 4.5~7.5g / m 2 , 5.0~10.5g / m 2 , 5.0~11.0g / m 2 , 5.0~12.0g / m 2 Or 5.0 to 15.0 g / m 2 The separator may be present at any density or add-on level.

[0103] The additives may also be applied by immersing the battery separator in a solution of the additive or additive (solvent bath addition) and removing the solvent when necessary (e.g., by drying). In this way, the application of the additive may be combined with an extraction that is often applied, for example, during the preparation of the membrane. Another preferred method is to spray the additive, dip coat, roller coat or curtain coat onto the surface of the separator.

[0104] In certain embodiments described herein, small amounts of anionic or nonionic surfactants are added to the separators of the present invention. In such instances, desirable characteristics may include low total organic carbon and / or low volatile organic compounds (due to the low amount of surfactant) can produce desirable separators of the present invention of this embodiment.

[0105] Manufacturing / Thickness As stated, the press or calendar may be engraved to create ribs, grooves, textured areas, serrated or serrated ribs, battlemented or battlemented ribs, broken ribs, Angular ribs, linear ribs, or curved or sinusoidal ribs, embossments, dimples, and the like may be provided and extend into or out of the microporous membrane or combinations thereof.

[0106] In some embodiments, the porous separator membrane has a backweb thickness of about 50 μm to 1.0 mm, 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. Backweb (However, in some embodiments, the backweb thickness may be as small as 50 μm. Backweb In a specific embodiment, the back web thickness is 50 μm to 75 μm. Backweb can be about 125 μm±75 μm or less.

[0107] In certain embodiments, the porous membrane can have a base web thickness TBASE of about 50 μm to 1.0 mm, about 50 μm to 750 μm, about 100 μm to 750 μm, about 200 μm to 750 μm, about 200 μm to 500 μm, about 150 μm to 500 μm, about 250 μm to 500 μm, about 250 μm to 400 μm, or about 250 μm to 350 μm. In certain embodiments, the base web thickness TBASE can be about 200 μm ± 35 μm or less.

[0108] puncture resistance In certain selected embodiments, the exemplary separator may be characterized by an increased puncture resistance. For example, the puncture resistance may be about 9N or more, 9.5N or more, 10N or more, 10.5N or more, 11N or more, 11.5N or more, 12N or more, 12.5N or more, 13N or more, 13.5N or more, 14N or more, 14.5N or more, 15N or more, 15.5N or more, 16N or more, 16.5N or more, 17N or more, 17.5N or more, 18N or more, 18.5N or more, 19N or more, 19.5N or more, or 20N or more. In certain embodiments, the exemplary separator may be preferably specified with an average puncture resistance of about 9N to 20N or more, about 11N to 20N or more.

[0109] Puncture resistance may be measured as the force required to pierce a porous membrane using tip 200, as generally described in Figure 5. The piercing base on which the porous membrane is supported while tip 200 pierces the membrane may be generally described as a base having a straight hole of 6.5 mm diameter, generally 10 mm deep. The travel limit of the tip may be about 4 mm to 8 mm below the surface of the piercing base. The piercing tip 200 moves linearly through the membrane at a speed of about 5 mm / sec.

[0110] Electrical resistance In certain selected embodiments, the exemplary separator exhibits reduced electrical resistance, e.g., electrical resistance of about 200 mΩ·cm 2 , 180mΩ·cm 2 , 160mΩ·cm 2 , 140mΩ·cm 2 , 120mΩ·cm 2, 100mΩ·cm 2 , 80mΩ·cm 2 , 6 0mΩ cm 2 , 50mΩ·cm 2 , 40mΩ·cm 2 , 30mΩ·cm 2 or 20mΩ·cm 2 In certain selected embodiments, exemplary separators are preferred. Approximately 40mΩ cm 2 ~25mΩ cm 2 It may have the following preferred electrical resistance:

[0111] In order to perform the test on a sample separator for the ER test evaluation described in the present invention, the sample separator must first be prepared. For this purpose, the sample separator is preferably immersed in a bath of demineralized water, and then the water is boiled and the sample separator is placed in the boiling demineralized water bath. After 10 minutes of immersion, the separator is removed. After removal, excess water is shaken off the separator and it is placed in a bath of sulfuric acid having a specific gravity of 1.280 at 27°C ± 1°C. The separator is left in the sulfuric acid bath for 20 minutes. The separator is then prepared for testing of electrical resistance.

[0112] flexural stiffness In certain selected embodiments, the exemplary separator may be characterized by increased bending stiffness in the width direction. Without wishing to be bound by theory, it is believed that increased bending stiffness in the width direction improves the separator's ability to be processed during the manufacture of lead-acid batteries.

[0113] For example, embodiments of the separator may have a bending stiffness of about 20 mN or more, 21 mN or more, 22 mN or more, 23 mN or more, 24 mN or more, 25 mN or more, 26 mN or more, 27 mN or more, 28 mN or more, 29 mN or more, 30 mN or more, 31 mN or more, 32 mN or more, 33 mN or more, 34 mN or more, 35 mN or more, 36 mN or more, 37 mN or more, 38 mN or more, 39 mN or more, 40 mN or more, 41 mN or more, 42 mN or more, 43 mN or more, 44 mN or more, 45 mN or more. In certain embodiments, exemplary separators may be defined by a puncture resistance of about 20 mN to 40 mN or more, or more preferably about 25 mN to 45 mN or more.

[0114] The bending stiffness in the cross direction may be measured as the force required to bend the sample. Figure 6 shows the test setup used to measure bending stiffness. To measure this value, it may be preferable to cut a 150 mm separator sample piece into a 10.0 mm rectangle. To perform the test, the 150 mm edge of the sample is clamped along its length. A force is applied at a bending length of 5 mm. The bending stiffness is measured by the force required to bend the sample at a bending angle α of 30°. The bending angle α is measured by a plane passing through the sample during clamping and application of the force and the same plane at the end of the test.

[0115] Oxidative Stability In certain selected embodiments, the exemplary separator may be characterized by improved and higher oxidation resistance. The oxidation resistance is measured by elongation of a specimen of a sample separator in the width direction after prolonged exposure to lead acid battery electrolyte. For example, the exemplary separator may have an elongation of about 100% or more, 150% or more, 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more at 40 hours. In certain embodiments, the exemplary separator may have a preferred oxidation resistance or elongation of about 100% or more at 40 hours. Furthermore, the exemplary separator may have an elongation of about 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more at 20 hours. In certain embodiments, the exemplary separator may have a preferred oxidation resistance or elongation of about 200% or more at 20 hours.

[0116] To test the sample for oxidation resistance, a sample specimen 400 of the exemplary separator is first cut into the shape generally depicted in Figure 7 A. The specimen 400 is placed in a sample holder generally as shown in Figure 7B.

[0117] The first sample was tested in the dry state at time = 0 hours for % elongation to break. The elongation is based on a distance of 50 mm measured from points A and B in Figure 7A. For example, if points A and B elongate to a distance of 300%, then the final distance between A and B is 150 mm.

[0118] The extension test is designed to simulate long term exposure to the electrolyte of a short term cycled battery. The sample 400 is first fully immersed in isopropanol, drained, and then immersed in water for 1-2 seconds. The sample is then immersed in the electrolyte. The solution is, in turn, immersed in the electrolyte for 36 A 100 ml solution of 1.28 specific gravity sulfuric acid, 35 ml of 1.84 specific gravity sulfuric acid, followed by 105 ml of 35% hydrogen peroxide is added. The solution is held at 80°C and the sample is immersed in the solution for an extended period of time. The sample may be tested for extension over a period of time, e.g., 20 hours, 40 hours, 60 hours, 80 hours. To perform this interval test, the sample 400 is removed from the 80°C electrolyte bath and placed under lukewarm running water until the acid is removed. A test for extension may be performed.

[0119] In at least selected embodiments, the disclosure or invention relates to improved battery separators, low ER or high conductance separators, improved lead acid batteries, e.g., flooded lead acid batteries, high conductance batteries, and / or improved vehicles including such batteries, and / or methods of making or using such separators or batteries and / or combinations thereof. In at least certain embodiments, the disclosure or invention relates to improved lead acid batteries incorporating the improved separators and exhibiting increased conductance. EXAMPLES

[0120] Table 1 details the parameters of an exemplary battery separator of the present disclosure.

[0121] [Table 1]

[0122] Table 2 shows the parameters of exemplary battery separators of the present disclosure. Improved Separator #1 represents the first attempt to make a separator of the present invention, and Improved Separator #2 represents an exemplary separator made from a refinement process.

[0123] [Table 2]

[0124] Table 3 details a comparison of an exemplary Improved Separator #2, Control Separator #1 and Control Separator #2, both of which are commercially available lead acid battery separators.

[0125] [Table 3]

[0126] conclusion The improved separator is useful in a variety of battery applications, particularly lead acid and lead acid battery applications. The battery may be a flooded battery, and may be a tubular or flat battery. The battery may be used in motive applications, such as batteries for golf carts (sometimes also called golf cars), or other deep cycle applications, such as solar or wind energy batteries.

[0127] Additionally, the inventive battery separators disclosed and described herein provide improved deep cycle batteries for use with more consistent and lower end of charge (EOC) currents. Maintaining a lower EOC current allows the improved batteries described herein to suppress antimony poisoning. As an example, over the life of a new deep cycle lead acid battery, more antimony is present in the battery, which means that the EOC current can increase over the life of the battery, thereby increasing the water consumption of the battery and decreasing the overall cycle life performance of the battery. The inventive separators described herein mean that the EOC current remains more constant over the cycle life of the battery, thereby showing reduced Sb poisoning.

[0128] Additionally, the improved battery separators described herein also provide deep cycle flooded lead acid batteries that exhibit reduced floating charge currents at steady state potential than batteries made using previously known separators, reduce the voltage and / or energy required to return a deep cycled battery to full charge than batteries made using previously known separators, provide overall improved voltage control than batteries made using previously known separators, and / or reduce grid corrosion than batteries made using previously known separators.

[0129] In selected embodiments of the present invention, about 130 g / m 2 A lead acid battery separator having the following basis weight and a widthwise bending stiffness of about 25 mN or greater can be provided.

[0130] In certain other selected embodiments of the present invention, a lead acid battery separator may be provided having a cross-machine bending stiffness of about 25 mN or less and a backweb thickness of about 125 μm or less.

[0131] In some embodiments of the present invention, the concentration is about 40 mΩ·cm 2 A separator can be provided having a porous membrane having an electrical resistance of about 1.0 N or less, an average puncture resistance of about 11.0 N or more, a 20 hour oxidation resistance of about 200% or more, a 40 hour oxidation resistance of about 100% or more, a backweb thickness of about 125 μm or less, a residual oil amount of about 20% or less, and a residual oil amount of about 10% or more.

[0132] In another aspect of the invention, the lead acid battery separator may have at least one array of ribs, which may have at least one of the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, solid or broken zigzag arranged curved or sinusoidal ribs, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

[0133] In selected embodiments, the separator may have a first array of ribs extending from a first backweb surface having a first rib height measured from the first backweb surface, a second array of ribs extending from a second backweb surface substantially perpendicular to the first array of ribs and having a second rib height measured from the second backweb surface, and may have a base web thickness of about 200 μm or less. The second array of ribs may have a height of about 75 μm or less and a backweb thickness of about 100 μm or less.

[0134] An exemplary separator can have an overall thickness of about 400 μm to about 2.0 mm.

[0135] In certain exemplary embodiments, the lead acid battery separator may have solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs that extend substantially in the lengthwise direction of the porous membrane, transverse ribs that extend substantially in the width ... The surface may have a first array of ribs from the group consisting of elongated cross ribs, serrated, serrated ribs, battlemented or battlemented ribs, curved or sinusoidal ribs arranged in a solid or broken zigzag pattern, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini ribs or cross mini ribs and combinations thereof.

[0136] In other selected embodiments, the lead acid battery separator may have a second array of ribs from the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, curved or sinusoidal ribs arranged in a solid or broken zigzag manner, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs and combinations thereof.

[0137] In selected embodiments, the present invention provides a lead acid battery having a separator substantially as described herein. The battery can be a flat battery, a tubular battery, a flooded lead acid battery, an enhanced flooded lead acid battery, a deep cycle battery, an absorbent glass mat battery, a tubular battery, an inverter battery, a vehicle battery, a starting-lighting-ignition ("SLI") battery, an idle-start-stop ("ISS") battery, a car battery, a truck battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid-electric vehicle battery, an electric vehicle battery, an e-rickshaw battery, an e-bike battery, or a marine battery.

[0138] The battery may be operated in a partial state of charge during operation, at rest, or during all of the aforementioned cycles.

[0139] In certain selected embodiments, the present invention provides a vehicle equipped with a lead acid battery having a separator substantially as described herein, the vehicle may be a car, truck, motorcycle, all-terrain vehicle, forklift, golf cart, idle-start-stop vehicle, hybrid-electric vehicle, electric vehicle, e-rickshaw, e-bike, or watercraft.

[0140] Provided are new or improved separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, methods, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, cells, systems, and / or batteries, battery separators having reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof, improved separators for enhanced flooded batteries, separators having reduced ER, improved puncture strength, improved separator CMD stiffness, reduced basis weight, or combinations thereof, separators including or exhibiting reduced ER, improved puncture strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof, and for use in flat batteries, tubular batteries, SLI and HEV for vehicles. ISS applications, deep cycle applications, golf cars or golf carts, and e-rickshaw batteries, batteries operating at partial state of charge ("PSOC"), inverter batteries, storage batteries for renewable energy resources and combinations thereof, and / or as shown, claimed or described herein.

[0141] In at least selected embodiments, aspects, or subjects, new or improved separators, battery separators, enhanced flooded battery separators, batteries, cells, and / or separators are provided. The present disclosure or invention relates to a novel or improved battery separator for enhanced flooded batteries, the separator having reduced ER, improved pin strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof. The present disclosure or invention relates to an improved separator for enhanced flooded batteries, the separator having reduced ER, improved pin strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, or combinations thereof. In at least certain embodiments, the present disclosure or invention relates to a novel or improved battery separator for enhanced flooded batteries, the separator having reduced ER, improved pin strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, or combinations thereof. In at least certain embodiments, separators are provided that include or exhibit reduced ER, improved pin strength, improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof. In at least certain embodiments, separators are provided for flat battery cells, tubular batteries, vehicle SLI and HEV ISS applications, deep cycle applications, golf car or golf cart, and e-rickshaw batteries, batteries operating at partial state of charge ("PSOC"), inverter batteries, and renewable energy resource storage batteries, and combinations thereof.

[0142] In at least selected embodiments, the present disclosure or invention relates to new or improved membranes, separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same, and / or methods of making and / or using such separators, battery separators, enhanced flooded battery separators, batteries, cells, systems, and / or vehicles using same. In at least certain embodiments, the present disclosure relates to new or improved enhanced flooded lead acid battery separators for inverter batteries, flooded batteries for deep cycle applications, automotive start light ignition ("SLI") batteries, batteries for idle-start-stop ("ISS") applications, e.g., hybrid-electric vehicles, and / or vehicle batteries such as enhanced flooded batteries ("EFBs"), and / or improved methods of making and / or using such improved separators, cells, batteries, systems, vehicles, and the like. In at least certain embodiments, the disclosure or invention relates to improved separators for enhanced flooded batteries, and / or improved methods of making, testing, and / or using batteries having such improved separators. In at least selected embodiments, the disclosure or invention relates to separators, particularly separators for enhanced flooded batteries having reduced separator electrical resistance ("ER"), reduced separator thickness, increased separator pin puncture strength, improved separator cross-machine direction ("CMD") stiffness, improved oxidation resistance, reduced separator basis weight, increased separator hydration, or combinations thereof. Further disclosed herein are methods, systems, and battery separators that increase battery life, reduce water loss, increase hydration, reduce internal resistance, and / or improve at least the uniformity of enhanced flooded batteries.In at least certain embodiments, the present disclosure or invention relates to an improved separator for enhanced flooded batteries, the separator comprising one or more performance enhancing additives or coatings, reduced electrical resistance, reduced caliper, increased pin puncture strength, improved CMD stiffness, improved oxidation resistance, reduced basis weight, or a combination thereof.

[0143] In at least certain possible preferred embodiments, aspects or subjects, membranes, separators or separators having novel configurations and / or improved combinations of properties are provided. Related batteries, methods and systems are also provided. In certain embodiments, new or improved separators, battery separators, enhanced flooded battery separators, batteries, cells and / or separators, uses of enhanced flooded battery separators, cells and / or batteries are provided. Further provided herein are reduced ER, improved puncture strength, improved Disclosed are methods, systems, and battery separators having improved separator CMD stiffness, improved oxidation resistance, reduced separator thickness, reduced basis weight, and combinations thereof. In at least certain embodiments, the separators are provided for flat batteries, tubular batteries, vehicle SLI and HEV ISS applications, deep cycle applications, golf car or golf cart, and e-rickshaw batteries, batteries operating at partial state of charge ("PSOC"), inverter batteries, and renewable energy resource storage batteries, and combinations thereof.

[0144] In at least certain possible preferred embodiments, aspects or objects, the following is provided or disclosed: Approximately 140g / m 2 A lead acid battery separator comprising at least one membrane having a basis weight of about 1000 g / m2 and a width-to-width bending stiffness of about 25 mN or greater.

[0145] The separator mentioned above has a membrane weight of about 135 g / m 2 and a bending stiffness in the cross direction of about 25 mN or more.

[0146] The separator mentioned above has a membrane weight of about 130 g / m 2 and a bending stiffness in the cross direction of about 25 mN or more.

[0147] The separator mentioned above has a membrane resistance of about 40 mΩ cm 2 It has an average electrical resistance of about 9.0 N or more and an average puncture resistance of about 9.0 N or more.

[0148] The separator mentioned above has a membrane resistance of about 40 mΩ cm 2 It has the following electrical resistance:

[0149] The aforementioned separator has a membrane having an average puncture resistance of about 10.0 N or greater.

[0150] The aforementioned separator has a membrane having an average puncture resistance of about 12.0 N or greater.

[0151] The aforementioned separator has a membrane having an average puncture resistance of about 14.0 N or greater.

[0152] The invention may be embodied in other forms without departing from its spirit or essential characteristics, and therefore, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of the invention.

[0153] The foregoing structures and methods have been presented for illustrative purposes only. The examples disclose exemplary embodiments, including the best mode, and include examples of making, using, and implementing the incorporated methods of the apparatus or systems used to enable one of ordinary skill in the art to practice the invention. 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 sequence that is physically possible. The patentable scope of the invention is defined by the appended claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal words of the claims, or if they include equivalent structural elements that have insubstantial differences from the literal words.

[0154] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, but are intended as illustrations of a few aspects of the claims. Functionally equivalent compositions and methods are intended to be within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to be within the scope of the appended claims. Moreover, while only certain representative compositions and methods disclosed herein have been specifically described, other combinations of compositions and method steps are intended to be within the scope of the appended claims even if not specifically recited. Thus, although a combination of steps, elements, components or ingredients may be explicitly recited herein, other combinations of steps, elements, components or ingredients are included even if not explicitly recited.

[0155] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include the plural unless the content clearly dictates otherwise. Ranges may be expressed herein, such as from "about" or "approximately" to a particular value and / or to "about" or "approximately" to another particular value. When such a range is expressed, another embodiment includes the one particular value and / or the other particular value. Similarly, when values ​​are expressed as approximations, by use of "about," in advance, it is understood that the particular value forms another embodiment. It is further understood that each endpoint of the range is both significant in relation to the other endpoint, and independent of the other endpoint. "Optional" or "optionally" may or may not result in the subsequently described event or circumstance, and the description includes instances in which the event or circumstance occurs and instances in which the event or circumstance does not occur.

[0156] Throughout the description and claims of this specification, the term "comprise" and variations of that term, such as "comprising" and "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 and disclose more detailed embodiments of the present invention. "Exemplary" means "an example of" and is not intended to convey depictions of preferred or ideal embodiments. Similarly, "e.g., "etc." is not used in a limiting sense, but is used for purposes of explanation or illustration.

[0157] Unless otherwise noted, geometries, dimensions, and the like used in the specification and claims are to be construed in light of the doctrine of equivalents but not in light of the scope of the claims, at the very least, some significant digits and ordinary rounding approaches.

[0158] 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 belongs. The publications mentioned herein and the material described therein are specifically incorporated by reference.

[0159] Furthermore, the invention illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

Claims

1. Approximately 130g / m ２ and a widthwise bending stiffness of about 25 mN or more.

2. Approximately 40 mΩ・cm ２ 2. The lead acid battery separator of claim 1 having an electrical resistance of:

3. 10. The lead acid battery separator of claim 1 having an average puncture resistance of about 11.0 N or greater.

4. 10. The lead acid battery separator of claim 1 having a 20 hour oxidation resistance of about 200% or greater.

5. 10. The lead acid battery separator of claim 1 having a 40 hour oxidation resistance of about 100% or greater.

6. 10. The lead acid battery separator of claim 1 having a porous membrane having a thickness of about 125 μm or less.

7. 10. The lead acid battery separator of claim 1 having an oil residual content of about 20% or less.

8. 10. The lead acid battery separator of claim 1 having a porous membrane with a residual oil content of about 10% or more.

9. 2. The lead acid battery separator of claim 1 having at least one array of ribs, wherein said at least one array of ribs is present in at least one of the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, crenellated ribs, battlemented or battlemented ribs, solid or broken zigzag arranged curved or sinusoidal ribs, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

10. 1. A lead acid battery separator having a cross-machine bending stiffness of about 25 mN or more and 40 mN or less, and a backweb thickness defined as the distance between a first backweb surface and a second backweb surface, said backweb thickness being about 125 μm or less.

11. a first array of ribs extending from said first backweb surface and having a first rib height measured from said first backweb surface; a second array of ribs extending from said second backweb surface, substantially perpendicular to said first ribs, and having a second rib height measured from said second backweb surface; the porous membrane having a base web thickness defined as the sum of the backweb thickness and the height of the second ribs; 11. The lead acid battery separator of claim 10, wherein said base web thickness is less than or equal to about 200 μm.

12. 12. The lead acid battery separator of claim 11 having a total thickness defined as the sum of said backweb thickness, said first rib height, and said second rib height, said total thickness being from about 400 μm to about 2.0 mm.

13. a first array of ribs extending from said first backweb surface and having a first rib height measured from said first backweb surface; a second array of ribs extending from said second backweb surface, substantially perpendicular to said first array of ribs, and having a second rib height measured from said second backweb surface; 11. The lead acid battery separator of claim 10, wherein said second rib has a height of about 75 μm or less.

14. 14. The lead acid battery separator of claim 13 having a total thickness defined as the sum of said backweb thickness, said first rib height, and said second rib height, said total thickness being from about 400 μm to about 2.0 mm.

15. 11. The lead acid battery separator of claim 10, wherein said backweb thickness is less than or equal to about 100 μm.

16. Approximately 130g / m ２ 11. The lead acid battery separator of claim 10 having a basis weight of:

17. Approximately 40 mΩ・cm ２ 11. The lead acid battery separator of claim 10 having an electrical resistance of:

18. 11. The lead acid battery separator of claim 10 having an average puncture resistance of about 11.0 N or greater.

19. 11. The lead acid battery separator of claim 10 having a 20 hour oxidation resistance of about 200% or greater.

20. 11. The lead acid battery separator of claim 10 having a 40 hour oxidation resistance of about 100% or greater.

21. At least one of the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, serrated, sawtooth ribs, battlemented or battlemented ribs, curved or sinusoidal ribs arranged in a solid or broken zigzag manner, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof.

11. The lead acid battery separator of claim 10 comprising a first array of bores.

22. a second of at least one rib from the group consisting of solid ribs, broken ribs, separate broken ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the lengthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, transverse ribs extending substantially in the widthwise direction of the porous membrane, cross ribs extending substantially in the widthwise direction of the porous membrane, serrated, sawtooth ribs, battlemented or battlemented ribs, solid or broken zigzag arranged curved or sinusoidal ribs, grooves, channels, textured areas, embossed patterns, dimples, porous, non-porous, mini-ribs or cross mini-ribs, and combinations thereof; 22. The lead acid battery separator of claim 21 comprising an array.

23. A lead acid battery comprising the lead acid battery separator according to any one of claims 1 to 22 and claims 31 to 33.

24. The battery may be a flat battery, a tubular battery, a flooded lead acid battery, an enhanced flooded 24. The lead acid battery of claim 23, selected from the group consisting of lead acid batteries, deep cycle batteries, absorbent glass mat batteries, tubular batteries, inverter batteries, vehicle batteries, starting-lighting-ignition ("SLI") batteries, idle-start-stop ("ISS") batteries, car batteries, truck batteries, motorcycle batteries, all terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid-electric vehicle batteries, electric vehicle batteries, e-rickshaw batteries, e-bike batteries, and marine batteries.

25. 24. The lead acid battery of claim 23, wherein the battery is operated in a partial state of charge.

26. 24. The lead acid battery of claim 23, wherein the battery operates during operation.

27. 24. The lead acid battery of claim 23, wherein the battery operates at rest.

28. A vehicle comprising the lead acid battery of claim 23.

29. 30. The vehicle of claim 28, wherein the battery operates in a partial state of charge.

30. 30. The vehicle of claim 28, wherein the vehicle comprises one selected from the group consisting of a car, 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 e-rickshaw, an e-bike, or a watercraft.

31. Approximately 140g / m ２ 1. A lead-acid battery separator comprising at least one membrane having a basis weight of at least about 1000 g / m2 and a cross-machine bending stiffness of at least about 25 mN.

32. The membrane has a thickness of about 135 g / m ２ 32. The separator of claim 31, having a basis weight of about 100% or less and a cross-machine stiffness of about 25 mN or greater.

33. The membrane has a thickness of about 130 g / m ２ 32. The separator of claim 31, having a basis weight of about 100% or less and a cross-machine stiffness of about 25 mN or greater.

34. The film has a resistance of about 40 mΩ·cm ２ 34. The separator of claim 31, having an electrical resistance of less than or equal to 100 MPa and an average puncture resistance of about 9.0 N or greater.

35. The film has a resistance of about 40 mΩ·cm ２ The separator according to any one of claims 31 to 33, having an electrical resistance of:

36. 34. The separator of any one of claims 31 to 33, wherein the membrane has an average puncture resistance of about 10.0 N or greater.

37. 34. The separator of any one of claims 31-33, wherein the membrane has an average puncture resistance of about 12.0 N or greater.

38. 34. The separator of any one of claims 31-33, wherein the membrane has an average puncture resistance of about 14.0 N or greater.

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