Lead Acid Battery Separators, Battery Systems, and Related Methods

Abstract

A compressible battery separator having the ability to accommodate varying spacing between electrodes in a lead acid battery. Battery separators, battery cells, batteries, systems, and methods of manufacture and use are disclosed herein.

Description

[0001] Field

[0002] The present disclosure is directed to new or improved separators for various lead acid batteries and / or systems. Additionally, the exemplary embodiments disclosed herein are directed to new or improved battery separators, battery cells incorporating the same, batteries incorporating the same, systems incorporating the same, and / or methods of making and / or using the same, and / or the like, and / or combinations thereof.

[0003] Background

[0004] Exemplary lead acid batteries have a positive terminal and a negative terminal. Inside the battery is an array of alternating positive and negative electrodes, with a separator interleaved between each electrode. Alternatively, either the positive or negative electrode may be encapsulated within a separator envelope, bag, sleeve, etc. The positive electrode is in electrical communication with the positive terminal, and the negative electrode is in electrical communication with the negative terminal. The positive electrode has a lead dioxide (PbO2) grid typically doped with positive active material (PAM). The negative electrode has a lead (Pb) grid typically doped with negative active material (NAM). Both PAM and NAM contribute to increasing the functionality of the electrodes. The positive and negative grids may be provided as an alloy having at least one of antimony, calcium, tin, selenium, and / or the like, and / or combinations thereof.

[0005] The positive electrode, negative electrode, and separator are substantially immersed in an aqueous electrolyte solution. The electrolyte can be, for example, a solution of sulfuric acid (H2SO4) and water (H2O). The electrolyte solution can have, for example, a specific gravity of about 1.28, with a variation range of about 1.215 to 1.300.

[0006] The purpose of the separator is to separate the electrodes from each other and electrically insulate them so as not to short circuit the battery, but still maintain ionic conduction between the electrodes through the electrolyte, which is necessary for the electrochemical reactions of the battery. Therefore, the separator must be non-conductive but porous enough to allow ionic conduction. If the separator is too porous or has too large pores, dendrites may form large enough to bridge the gap between the electrodes, thus short circuiting the battery. Very large pores can cause direct physical contact between the electrodes.

[0007] The manufacturing process of some lead acid batteries is difficult to control, resulting in variations in the spacing between the electrodes. Additionally, some mobility applications may cause the electrodes to vibrate and change the spacing. The prior art cannot address or solve these needs and concerns.

[0008] As discussed, there is still a need to provide separators with variable thickness to accommodate variable spacing between the electrodes. As of the filing of this application, the inventors are aware of no such battery separator that can provide a variable thickness that can accommodate changing and / or altered electrode spacing. Accordingly, the present invention is intended to at least meet these and other heretofore unmet needs.

[0009] Overview

[0010] For at least certain applications or batteries, details of one or more exemplary embodiments, aspects, or objects of the present invention provide a battery separator having a variable total thickness, such as where the total thickness varies as a function of the pressure applied to the separator. Other features, objects, and advantages of the present invention provide reduced battery failures, increased battery cycle life, and / or improved performance. More specifically, there remains a need to provide a separator that can accommodate a changing electrode spacing during at least one of the production process of the battery and / or during its use after manufacture.

[0011] Details of one or more exemplary embodiments, aspects, or objects are set forth in the detailed description of the invention and the claims that follow. From the detailed description of the invention and the claims that follow, other features, objects, and advantages will be apparent. According to one or more selected embodiments, aspects, or objects, the present disclosure or invention at least solves the difficulties, problems, or needs enumerated herein and, in some cases, provides solutions that are surprisingly and unexpectedly beyond the needs and expectations.

[0012] According to at least certain exemplary embodiments, objects, or aspects, the present disclosure or invention provides a new or improved separator, battery cell, battery, system, method of making, using, and / or applying such new or improved separator, battery cell, battery, and / or system that at least overcomes the above problems. For example, at least certain exemplary embodiments, objects, or aspects provide a battery having a separator that can accommodate electrodes having a changing spacing and provide a battery having a separator with a variable thickness.

[0013] According to at least selected exemplary embodiments, aspects, or objects, the present disclosure or invention provides a separator in which the composition and physical properties and characteristics are synergistically combined to solve, in a surprising and unexpected manner, previously unmet needs in the lead - acid battery industry through an improved battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a battery using a separator as described herein, solving, in a surprising and unexpected manner, previously unmet needs in the lead - acid battery industry through an improved lead - acid battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a system using a battery as described herein, solving, in a surprising and unexpected manner, previously unmet needs in the lead - acid battery industry through an improved system (which uses the invented lead - acid battery that uses the invented separator as described herein).

[0014] According to at least certain embodiments, the present disclosure or invention is directed to new or improved separators, battery cells, batteries, systems, and / or methods of manufacturing and / or using and / or applying such new separators, battery cells, batteries, and / or systems. According to at least certain embodiments, the present disclosure or invention is directed to new or improved battery separators for use in: lead-acid batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, flat plate batteries, tubular batteries, deep cycle batteries, batteries operating in a partial state of charge (PSoC), valve-regulated lead-acid (VRLA) batteries, gel batteries, absorbent glass mat (AGM) batteries, inverter batteries, stationary batteries, batteries used during movement, energy storage devices for power generation (such as through steam turbine generators, such as in coal- and / or gas-fired power plants and / or nuclear power plants), energy storage devices for power generation through solar, wind, hydro, or other alternative and / or renewable energy sources, general energy storage batteries, uninterruptible power supply (UPS) batteries, batteries with high cold cranking amps (CCA) requirements, vehicle batteries (such as starting-lighting-ignition (SLI) vehicle batteries, idle start-stop (ISS) vehicle batteries), marine batteries, automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart (also known as golf car) batteries, hybrid electric vehicle (HEV) batteries, electric vehicle batteries, light electric vehicle batteries, neighborhood electric vehicle (NEV) batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, electric scooter batteries, and / or the like and / or combinations thereof. According to selected embodiments, the present disclosure or invention is directed to battery separators for use in systems or vehicles incorporating the batteries mentioned above. According to at least certain aspects, the present disclosure or invention is directed to improved methods for manufacturing and / or using such improved separators, battery cells, batteries, systems, and / or the like.

[0015] According to a first selected embodiment of the present invention, the battery separator is provided with a porous membrane backing web having a first surface and a second surface, the second surface being on the side opposite the first surface. The separator is also provided with an array of ribs consisting of a first plurality of ribs extending from the first surface and a second plurality of ribs extending from the second surface. At least a portion of the first rib array is not disposed opposite any of the second plurality of ribs disposed on the second surface.

[0016] According to some exemplary aspects of the present invention, the rib array may or may not be equally spaced apart. Additionally, either or both of the first plurality of ribs and the second plurality of ribs may or may not be equally spaced apart. These rib spacings may exist in any combination.

[0017] According to at least one aspect of the present invention, the rib array may be arranged such that one or more of the first plurality of ribs alternate with one or more of the second plurality of ribs across the width of the separator.

[0018] In some aspects, the separator may have micro ribs disposed on one or both surfaces of the separator. These micro ribs (or negative current collectors or NCRs) may be arranged between a first and a second plurality of ribs in the processing direction of the separator or across the processing direction of the separator. The micro ribs may have a height of from about 25 μm to about 75 μm.

[0019] In selected embodiments, the first plurality of ribs may be substantially parallel to each other, the second plurality of ribs may be substantially parallel to each other, and / or the first plurality of ribs may be substantially parallel to the second plurality of ribs. The first plurality of ribs and the second plurality of ribs may be substantially parallel to the processing direction of the separator.

[0020] In a selected preferred aspect of the present invention, the first plurality of ribs and / or the second plurality of ribs may be spaced apart by the following distances: between about 4 mm and about 18 mm, between about 5 mm and about 16 mm, or between about 6 mm and about 14 mm. The spacing may be 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm or 20 mm.

[0021] According to a particular preferred embodiment of the present invention, the battery separator may have a relaxed state (where the porous film backing is generally flat) and a compressed state different from the relaxed state (where the porous film backing is generally warped).

[0022] According to a selected preferred embodiment, the separator has a total thickness defined by the distance between a plane formed by the tips of the first plurality of ribs and a plane formed by the tips of the second plurality of ribs. In a selected embodiment, the total thickness in the compressed state is at least about 500 μm. In a selected embodiment, the total thickness in the compressed state does not exceed about 2.0 mm. In other embodiments, the total thickness in the relaxed state does not exceed about 3.0 mm.

[0023] In the relaxed state, the total thickness may be measured as the sum of the thickness of the porous film backing, the height of the first plurality of ribs, and the height of the second plurality of ribs. In this case, the total thickness in the relaxed state does not exceed about 3.0 mm.

[0024] In a particular exemplary embodiment, the first plurality of ribs have a first rib height of from about 200 μm to about 1.5 mm. Additionally, the second plurality of ribs have a second rib height of from about 200 μm to about 1.5 mm.

[0025] In some preferred embodiments, the first plurality of ribs have a first rib height, and the second plurality of ribs include a second rib height. The first rib height is equal to from about 25% to about 400% of the second rib height.

[0026] Another aspect of the present invention provides a porous film backing web having a thickness between about 125 μm and about 250 μm.

[0027] In yet another aspect of the present invention, the battery separator may have a composition that includes at least one of the following: polymers, thermoplastics, polyvinyl chloride (PVC), phenolic resins, natural or synthetic rubbers, synthetic wood pulp, lignin, glass fibers, synthetic fibers, cellulose fibers, and / or combinations thereof. Natural or synthetic rubbers may include one or more of the following: rubber, latex, natural rubber, synthetic rubber, cross-linked or non-cross-linked natural or synthetic rubbers, vulcanized or unvulcanized rubbers, shredded or ground rubber, polyisoprene, methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers (such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber) and / or combinations thereof.

[0028] In some aspects of the present invention, the battery separator may further have a filler that is at least one of the following: silica, dry-processed finely divided silica, precipitated silica, amorphous silica, highly friable silica, alumina, talc, fish meal, fish bone meal, barium sulfate (BaSO4), carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high-surface-area carbon black, graphene, high-surface-area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide, and / or combinations thereof.

[0029] In other aspects of the present invention, the battery separator may further have a coating that is at least one of the following: barium sulfate (BaSO4), zinc, zinc sulfate, carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high-surface-area carbon black, graphene, high-surface-area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide, and / or combinations thereof.

[0030] In yet another exemplary aspect of the present invention, one or both of the first plurality of ribs and the second plurality of ribs are at least one of the following: uninterrupted ribs, discrete interrupted ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the cross-processing direction of the porous membrane, cross-cut ribs extending substantially in the cross-processing direction of the porous membrane, cross ribs (or negative cross ribs or NCRs) extending substantially in the cross-processing direction of the porous membrane, discrete teeth or toothed ribs, serrated, serrated ribs, stack-shaped or stacked ribs, curved or sinusoidal ribs, arranged in an uninterrupted or interrupted zigzag pattern, grooves, channels, textured areas, bumps, columns, embossments, pits, porous, non-porous, micro ribs or micro cross ribs, and combinations thereof. In another aspect, the exemplary battery separator may have negative cross ribs (NCRs).

[0031] In a selected preferred embodiment of the present invention, a lead-acid battery is provided with one or more positive electrodes and one or more negative electrodes, and an embodiment of a battery separator as generally described and claimed herein disposed therebetween.

[0032] In a particular aspect of the present invention, the lead-acid battery can be one of the following: flooded lead-acid battery, enhanced flooded lead-acid battery (EFB), flat plate battery, tubular battery, deep cycle battery, battery operating in a partial state of charge (PSoC), valve-regulated lead-acid (VRLA) battery, gel battery, absorbent glass mat (AGM) battery, inverter battery, stationary battery, battery used during exercise, energy storage battery for power generation, general energy storage battery, uninterruptible power supply (UPS) battery, battery with high cold cranking amperage (CCA) requirements, vehicle battery (such as a starting-lighting-ignition (SLI) vehicle battery, idle start-stop (ISS) vehicle battery), marine battery, automotive battery, truck battery, motorcycle battery, all-terrain vehicle battery, forklift battery, golf cart (also known as a golf car) battery, hybrid electric vehicle (HEV) battery, electric vehicle battery, light electric vehicle battery, neighborhood electric vehicle (NEV) battery, electric rickshaw battery, electric tricycle battery, electric bicycle battery, electric scooter battery, and / or the like and / or combinations thereof.

[0033] In certain preferred exemplary embodiments, the present invention can provide a vehicle, device, or system that uses a lead-acid battery as generally described and claimed herein, and the lead-acid battery uses a battery separator as generally described and claimed herein. The vehicle, device, or system can be at least one of the following: a power generation system (such as a steam turbine generator, such as a power plant using coal and / or gas, and / or a nuclear power plant), a power generation system that generates electricity through solar energy, wind energy, hydropower, or other alternative and / or renewable energy sources, an uninterruptible power supply (UPS), a vessel, an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart (also known as a golf car), a hybrid electric vehicle (HEV), an electric vehicle, a light electric vehicle, a neighborhood electric vehicle (NEV), an electric rickshaw, an electric tricycle, an electric bicycle, an electric scooter, and / or the like and / or combinations thereof.

[0034] In addition, a fiber mat can be provided. The mat can be one of the following: fiberglass, synthetic fiber, silica, at least one performance enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof, and can be non-woven, woven, mesh, flannel, netting, and combinations thereof.

[0035] In addition, the battery separator can be provided as slices, leaves, bags, sleeves, wrappers, envelopes, and hybrid envelopes with an opening at the bottom.

[0036] A first plurality of ribs can be further provided to enhance acid mixing in the battery, especially during battery movement. The separator can be arranged such that the first surface and the second surface are parallel to the direction in which the battery starts and stops moving. The separator can be provided with a mat adjacent to the positive electrode, negative electrode, or separator. The mat can be at least partially made of: fiberglass, synthetic fiber, silica, at least one performance enhancing additive, latex, natural rubber, synthetic rubber, and any combination thereof. The mat can be non-woven, woven, mesh, flannel, net-like, and combinations thereof.

[0037] In certain embodiments, the battery can operate at a depth of discharge between approximately 1% and approximately 99%.

[0038] According to at least selected exemplary embodiments, aspects, or objectives, the present invention at least solves, meets, and / or overcomes difficulties, needs, and / or problems that have heretofore not been solved, met, and / or overcome by the current state of the art. According to at least specific objectives, the present invention provides an improved separator, an improved battery using the improved separator, and / or an improved system using the improved battery, which at least overcomes and in some cases surprisingly and unexpectedly overcomes at least the above problems. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 is a schematic cross-sectional side view of a typical lead-acid battery having a plurality of alternating positive (+) and negative (-) electrodes with separators interposed therebetween.

[0040] Figure 2A shows a plan view of a typical separator having a first surface on which a plurality of ribs are disposed longitudinally and extend therefrom and are substantially parallel to the processing direction. Figure 2B shows Figure 2A a plan view of the separator shown in

[0041] Figure 3A is Figure 2A and and Figure 2B a side view of the separator depicted in Figure 3B is Figure 3A a side view of the separator depicted in

[0042] Figure 4 is a side view of an electrode / separator assembly having separators as depicted in Figure 2A and 2B and Figure 3A and 3B having major ribs in contact with the positive electrode and minor ribs in contact with the negative electrode.

[0043] Figure 5A and Figure 5B show plan views of two surfaces of an exemplary embodiment of the separator of the present invention. Figure 5A depicts a first surface having a first plurality of ribs disposed longitudinally and extending therefrom and being substantially parallel to the processing direction. Figure 5B shows a second surface opposite the first surface having a second plurality of ribs disposed longitudinally and extending therefrom and being disposed in substantially the same direction as the ribs on the first surface. Figure 5A and 5B further show that the first plurality of ribs and the second plurality of ribs are offset from each other and not aligned with each other.

[0044] Figure 6A and Figure 6B is Figure 5A and 5B a side view of an exemplary embodiment of the separator of the present invention shown in

[0045] Figure 7A and Figure 7B is a side view of an electrode / separator assembly having Figures 5A to 6B the exemplary embodiment of the invented separator given in Figure 7A shows an exemplary separator in a relaxed state. Figure 7B shows an exemplary separator in a compressed state.

[0046] Figure 8 and Figure 9 is a side view of an exemplary inventive embodiment of a separate invented separator.

[0047] Figure 10 is a plan view of an exemplary embodiment of the invented separator having micro transverse ribs.

[0048] Figure 11 is a plan view of an exemplary embodiment of the invented separator showing the serration tips on serrated ribs or stack ribs.

[0049] Figure 12 is a plan view of an exemplary embodiment of the invented separator having discrete protrusions instead of ribs.

[0050] Figure 13 is a graph showing the total separator thickness (μm) of 4 sample separators and a control separator at 4 compression stages.

[0051] Figure 14 is a graph showing the change in total thickness (μm) of 4 sample separators and a control separator from a previous compression stage.

[0052] Figure 15 is a graph showing the percentage change in total thickness of 4 sample separators and a control separator from a previous compression stage. DETAILED DESCRIPTION OF THE INVENTION

[0054] It should be understood that the drawings (or figures) depicted and described herein are not necessarily drawn to scale or in proportion to the actual embodiments, and for clarity, the dimensions of some features in the drawings may be exaggerated or reduced.

[0055] As battery manufacturers strive to control electrode spacing, and as batteries are subject to movement, vibration, and applications that cause the electrodes to rattle, there is still a need to provide battery separators that can accommodate changing electrode spacing.

[0056] According to at least certain exemplary embodiments, objectives, or aspects, the present disclosure or invention can provide new or improved separators, battery cells, batteries, systems, and methods of manufacturing, using, and / or applying such new or improved separators, batteries, battery cells, batteries, and / or systems. For example, at least certain exemplary embodiments, objectives, or aspects provide a battery having a separator that is adapted for electrodes with a smaller, compressed spacing as compared to typical batteries of the prior art, and provides a battery with reduced size and an increased power-to-volume ratio.

[0057] According to at least certain embodiments, the present disclosure or invention is directed to new or improved separators, battery cells, batteries, systems, and / or methods of manufacturing and / or using and / or applying such new separators, battery cells, batteries, and / or systems. According to at least certain embodiments, the present disclosure or invention is directed to new or improved battery separators for: lead-acid batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, flat-plate batteries, tubular batteries, deep-cycle batteries, batteries operating in a partial state of charge (PSoC), valve-regulated lead-acid (VRLA) batteries, gel batteries, absorbent glass mat (AGM) batteries, inverter batteries, energy storage devices for power generation (such as by steam turbine generators, such as by coal-fired and / or gas-fired power plants and / or nuclear power plants), energy storage devices for power generation by solar, wind, hydro, or other alternative and / or renewable energy sources, general energy storage batteries, uninterruptible power supply (UPS) batteries, batteries having a high cold-cranking current (CCA) requirement, vehicle batteries (such as starting-lighting-ignition (SLI) vehicle batteries, idle start-stop (ISS) vehicle batteries), automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart (also known as golf car) batteries, hybrid electric vehicle (HEV) batteries, electric vehicle batteries, light electric vehicle batteries, e-rickshaw batteries, e-trike batteries, e-bicycle batteries, e-scooter batteries, and / or the like. According to at least certain aspects, the present disclosure or invention is directed to improved methods for manufacturing and / or using such improved separators, battery cells, batteries, systems, and / or the like.

[0058] In addition, what is disclosed herein are exemplary battery separators, methods, and systems of the invention that are used to reduce battery size, increase the energy density of the battery, increase, enhance, or improve battery performance and / or battery life, increase, enhance, or improve acid accessibility at the electrodes, increase, enhance, or improve acid diffusion, reduce or mitigate battery failures, reduce or mitigate acid stratification, reduce or mitigate the formation and growth of dendrites, increase, enhance, or improve oxidative stability, optimize porosity, optimize tortuosity, improve, maintain, and / or reduce floating current, improve charge termination current, reduce the current and / or voltage required for deep cycle battery charging and / or full charging, improve charge acceptance, reduce internal resistance, reduce or mitigate antimony poisoning, increase wettability, improve uniformity within lead-acid batteries, improve cycle performance, and / or the like. According to at least particular embodiments, the present disclosure or invention is directed to an improved separator, where the new separator includes a relaxed or configured state and a compressed or configured state, new and improved rib designs, performance enhancing additives or coatings, improved fillers, negative cross ribs, and / or the like, and combinations thereof.

[0059] Now referring to Figure 1 , an exemplary lead-acid battery 50 is provided with an electrode / separator array 50a that is provided with alternating positive electrodes 52 and negative electrodes 54, and separators 100 that are interleaved between each positive electrode 52 and negative electrode 54. The electrode / separator array 50a is shown with leaf-shaped or sliced separators 100, however, it may alternatively be formed as a positive envelope (i.e., enclosing the positive electrode), a negative envelope (i.e., enclosing the negative electrode), a hybrid envelope, a bag, a sleeve, a wrapper, and / or the like, and / or combinations thereof.

[0060] The positive electrode 52 has a lead dioxide (PbO2) grid that is typically doped with positive active material (PAM). The negative electrode 54 has a lead (Pb) grid that is typically doped with negative active material (NAM). Both PAM and NAM contribute to improving the functionality of the electrodes. The positive grid and the negative grid may be formed as an alloy that has at least one of antimony (Sb), calcium (Ca), tin (Sn), selenium (Se), and / or the like or combinations thereof.

[0061] The exemplary lead-acid battery 50 is also provided with a positive terminal 51 and a negative terminal 53. The positive terminal 51 is in electrical communication with the positive electrode 52. Similarly, the negative terminal 53 is in electrical communication with the negative electrode 54. The terminals 51, 53 are typically disposed at the top or side of the battery 50.

[0062] The electrodes 52, 54 and the separator 100 are substantially immersed in the electrolyte 56. The electrolyte is preferably a solution of water and sulfuric acid (H2SO4). The electrolyte solution preferably has a specific gravity of about 1.28, in the range of about 1.215 to about 1.300.

[0063] The purpose of the separator is to separate the electrodes from each other and prevent electrical conduction between them (which would short-circuit the battery), but still maintain ionic conduction between the electrodes through the electrolyte, which is necessary for the electrochemical reactions of the battery. Therefore, the separator must be non-conductive but porous enough to allow ionic conduction. If the separator is too porous or has too large pores, dendrites large enough may form to bridge the gap between the electrodes and short-circuit the battery. Very large pores can result in direct physical contact between the electrodes.

[0064] Figure 1 The top and bottom of the exemplary battery 50 are marked. Figure 1 Also marked are the longitudinal or machine direction md arrow and the cross-machine direction cmd arrow, which correspond to the machine direction and the cross-machine direction of the separator 100. The machine direction md generally extends from the top to the bottom of the battery 50 and is substantially parallel to the separator 100, and the cross-machine direction cmd is substantially perpendicular to the machine direction md and substantially parallel to the separator 100.

[0065] Now referring Figure 2A and Figure 2B , a typical separator 100 is provided with a porous membrane backing web 102, which is a substantially flat web having two opposite major surfaces 102p, 102n, and as shown, has ribs 104, 106 extending from the opposite major surfaces 102p, 102n. Exemplary porous membranes can be microporous membranes (having pores less than about 5 μm, preferably less than about 1 μm), mesoporous membranes, or macroporous membranes (having pores greater than about 1 μm). The porous membrane preferably can have a submicron pore size up to 100 μm, and in certain embodiments, the pore size is between about 0.1 μm and about 10 μm. In certain embodiments, the porosity of the porous membranes described herein can be greater than about 50% to about 65%, and even up to or higher than about 70%, 75%, or even 80%. In certain selected embodiments, the porous membrane can be flat or have ribs 204, 206 extending from one or more of its major surfaces 102p, 102n.

[0066] Continuing to refer Figure 2A , a typical exemplary separator 100 is shown having a porous membrane backing web 102 and a plurality, series, array, or group of ribs 104, the ribs 104 being disposed on the first major surface 102p and extending from the first major surface 102p and being substantially aligned longitudinally (substantially aligned with the machine direction md of the separator 100). Referring Figure 2B , a typical exemplary separator 100 is shown having a porous membrane backing web 102 and a plurality, series, array, or group of ribs 106, the ribs 106 being disposed on the second major surface 102n and extending from the second major surface 102n and being laterally aligned substantially transversely (substantially aligned with the cross-machine direction cmd of the separator 100). Returning to referFigure 1 , the processing direction md is basically aligned with the battery 50 from top to bottom and is substantially parallel to the main surfaces 102p, 102n of the separator 100, while the cross-processing direction cmd is substantially orthogonally aligned with the processing direction and is substantially parallel to the main surfaces 102p, 102n of the separator 100. When shown in all figures, the processing direction is shown as an arrow line marked as md, and the cross-processing direction is shown as an arrow line marked as cmd.

[0067] As described above, a typical commercially available battery separator 100, such as some separators manufactured and sold, is provided with a porous film backing 102 having a first surface 102p and an opposite second surface 102n. When the separator 100 is disposed within a battery or battery cell assembly, the first surface 102p may be the surface facing the positive electrode; when the separator 100 is disposed within a battery or battery cell, the second surface 102n may be the surface facing the negative electrode. A plurality, series, array, or group of positive ribs 104 are typically provided on and extend from the first surface 102p (positive electrode surface), while a plurality, series, array, or group of negative ribs 106 are typically provided on and extend from the second surface 102n (negative electrode surface). The positive ribs 104 are sometimes referred to as main ribs because they are typically larger than the negative ribs 106, and the negative ribs 106 are sometimes referred to as secondary ribs. As shown in Figure 2A , 2B , 3A, 3B, and 4, the second plurality, series, array, or group of ribs 106 are shown as negative cross ribs having a height less than the height of the positive ribs and a smaller spacing than the spacing of the positive ribs.

[0068] Now refer to Figure 3A , 3B and 4 to define a typical commercially available separator 100 in terms of several dimensions. Figure 3A and 3B depict a typical commercially available separator 100 without a battery or battery cell assembly, while Figure 4 depicts a typical commercially available separator 100 within a battery or battery cell assembly. Figure 3A depicts and defines the positive rib spacing SpacingPos of the first plurality, series, array, or group of ribs 104 (i.e., positive ribs). For at least a portion, and possibly even most to all, of the first plurality of ribs 104 that span the separator width WidthSep, the positive rib spacing SpacingPos is typically fixed. Thus, the positive rib spacing SpacingPos can vary across the width WidthSep of the separator. Figure 3A and 3BThe height HeightPos of the first plurality of ribs 104 (i.e., the positive electrodes) and the height HeightNeg of the second plurality of ribs 106 (i.e., the negative electrodes), the backweb thickness ThicknessBW, and the overall thickness ThicknessOA are further depicted and defined (also shown as in Figure 4 ). The overall thickness ThicknessOA is generally the sum of the positive electrode rib height HeightPos, the negative electrode rib height HeightNeg, and the backweb thickness ThicknessOA. For a typical commercially available separator 100, the overall thickness ThicknessOA is substantially a constant value regardless of whether the separator 100 is disposed inside or outside a battery or battery cell assembly. For a given separator 100, the rib height dimensions HeightPos, HeightNeg can be variable. The overall thickness ThicknessOA is determined by the height dimension having the highest value. As shown, the rib height dimensions HeightPos, HeightNeg have fixed values for each respective height dimension. Figure 4 A separator 100 is shown that is disposed inside a battery cell assembly and is located between a positive electrode 52 and a negative electrode 54.

[0069] Now referring to Figures 5A to 9 , an exemplary embodiment of the inventive separator 200 of the present disclosure or invention is provided with a porous membrane backweb 202. The exemplary porous membrane of the exemplary inventive separator 200 can be a microporous membrane (having pores less than about 5 μm, preferably less than about 1 μm), a mesoporous membrane, or a macroporous membrane (having pores greater than about 1 μm). The porous membrane preferably can have a submicron pore diameter up to 100 μm, and in a particular embodiment, the pore diameter is between about 0.1 μm and about 10 μm. In a particular embodiment, the porous membrane porosity described herein can be greater than about 50% to about 65%, and even up to or higher than about 70%, 75%, or even 80%. In a particular selected embodiment, the porous membrane can be flat or have ribs 204, 206 extending from one or more of its major surfaces 202p, 202n.

[0070] The exemplary inventive separator 200 of the present disclosure or invention is provided with a porous membrane backsheet 202, which is a substantially flat sheet having two opposing major surfaces 202p, 202n. A first plurality, series, array or group of ribs 204 are provided on and extend from the first surface 202p, and a second plurality, series, array or group of ribs 204 are provided on and extend from the second surface 202n. When the separator 200 is disposed within a battery or battery cell assembly, the first surface 202p may be the surface facing the positive electrode. When the separator 200 is disposed within a battery or battery cell assembly, the second surface 202n may be the surface facing the negative electrode. Thus, when disposed within a battery or battery cell assembly, the first plurality, series, array or group of ribs 204 may be referred to as positive electrode ribs 204 and are adjacent to the positive electrode 52; when disposed within a battery or battery cell assembly, the second plurality, series, array or group of ribs 206 may be referred to as negative electrode ribs 206 and are adjacent to the negative electrode 54. As shown, the first plurality of ribs 204 and the second plurality of ribs 206 are substantially aligned and parallel with the processing direction of the separator 200 and are parallel to each other. Further, at least a portion of the first plurality of ribs 204 is offset and misaligned with any of the ribs of the second plurality of ribs 206. As Figures 5A to 9 shown, none of the first plurality of ribs 204 are aligned with any of the ribs of the second plurality of ribs 206.

[0071] Now referring to Figure 6A, an embodiment of the exemplary separator 200 is defined by a number of physical dimensions. The first plurality, series, array, or group of ribs 204 (i.e., the positive electrodes) have a height dimension HeightPos and a spacing dimension SpacingPos across the separator width WidthSep. For at least a portion of the first plurality of ribs 204, and possibly even for most to all of the separator width WidthSep, the positive electrode rib spacing SpacingPos can be fixed or constant. Thus, the positive electrode rib spacing SpacingPos can be fixed or constant and / or vary across the separator width WidthSep. When the positive electrode rib spacing SpacingPos is fixed or constant, the positive electrode ribs 204 are equidistantly arranged across the separator width WidthSep. As shown, the positive electrode rib spacing SpacingPos is fixed. The second plurality, series, array, or group of ribs 206 (i.e., the negative electrodes) have a height dimension HeightNeg and a spacing dimension SpacingNeg across the separator width WidthSep. For at least a portion of the second plurality of ribs 206, and possibly even for most to all of the separator width WidthSep, the negative electrode rib spacing SpacingNeg can be fixed or constant. Thus, the negative electrode rib spacing SpacingPos can be fixed or constant and / or vary across the separator width WidthSep. As shown, the negative electrode rib spacing SpacingPos is fixed. When the negative electrode rib spacing SpacingNeg is fixed or constant, the negative electrode ribs 206 are equidistantly arranged across the separator width WidthSep. The height dimensions HeightPos, HeightNeg are defined as the heights of the ribs 204, 206, which are measured from the respective surfaces 102p, 102n of the back web 202 from which the ribs 204, 206 extend. The height dimensions HeightPos, HeightNeg can be equal or unequal. Additionally, the height dimensions HeightPos, HeightNeg can be fixed or constant for all ribs - meaning all ribs have the same height. Conversely, the positive electrode rib height HeightPos can vary among the positive electrode ribs 204, and the negative electrode rib height HeightNeg can vary among the negative electrode ribs 204.

[0072] Continue to refer to Figure 6A, an exemplary new separator 200 embodiment is further provided with a total rib pitch dimension SpacingRib, which is the distance from one rib to the next rib, regardless of the side of the back web on which the rib is located. As shown, the positive rib pitch SpacingPos is equal to the negative rib pitch SpacingNeg. As further shown, the total rib pitch SpacingRib is fixed or constant for at least a portion or all of the separator width WidthSep, such that the ribs 204, 206 are generally equally spaced apart. However, the positive rib pitch SpacingPos can be equal to the negative rib pitch SpacingNeg while the total rib pitch SpacingRib is fixed or constant across the separator width WidthSep.

[0073] In at least certain selected embodiments of the new separator 200, the positive rib pitch dimension SpacingPos is preferably equal to the negative rib pitch dimension SpacingNeg. Additionally, the total rib pitch dimension SpacingRib is preferably equal to half of the positive and negative rib pitch dimensions SpacingPos, SpacingNeg.

[0074] Reference Figure 6B , an exemplary embodiment of the separator 200 is further defined by a total thickness ThicknessOA. The total thickness ThicknessOA is defined as the distance from a first plane 210 to a second plane 212. The first plane 210 is generally and substantially coplanar with the tips 211 of the first plurality of ribs 204. The second plane 212 is generally and substantially coplanar with the tips 213 of the second plurality of ribs 206. The tips 211, 213 of the ribs are defined as the points on the ribs 204, 206 that are furthest from the separator back web 202.

[0075] Now refer Figure 7A and Figure 7B , the exemplary new separator 200 is disposed between a positive electrode 52 and a negative electrode 54. Figure 7A An exemplary new separator 200 in a relaxed state within an electrode / separator assembly 50a is shown -- meaning the separator is not compressed. In Figure 7A , the new separator 200 has a total relaxed thickness ThicknessRelax. Figure 7B An exemplary new separator 200 in a compressed state within an electrode / separator assembly 50a is shown -- meaning the separator is compressed. In Figure 7B , the new separator 200 has a total compressed thickness ThicknessCompress. It can be understood that the compressed thickness ThicknessCompress is less than the relaxed thickness ThicknessRelax.

[0076] Now referFigure 8 , the exemplary new separator 200 is defined by a number of dimensions as generally described above. In a particular selected embodiment, the positive ribs 204 are spaced equidistantly at a fixed or constant spacing SpacingPos, while the negative ribs 206 are variably spaced at a variety of rib spacings Spacing1Neg, Spacing2Neg. Although the negative rib spacings Spacing1Neg, Spacing2Neg vary, the total rib spacing SpacingRib can be constant so that the ribs 204, 206 are spaced equidistantly.

[0077] Reference Figure 9 , the exemplary new separator 200 is defined by a number of dimensions as generally described above. In a particular selected embodiment, the positive ribs 204 are variably spaced at a variety of rib spacings Spacing1Pos, Spacing2Pos. The negative ribs 206 are spaced equidistantly at a fixed or constant spacing SpacingNeg. Figure 9 Configurations with varying total rib spacings are given. As shown, the entire ribs 204, 206 are variably spaced at a number of rib spacings Spacing1Rib, Spacing2Rib.

[0078] Although not shown in the figures, it is conceivable that not only one of the positive ribs 204 or the negative ribs 206 has a variety of rib spacings, but both the positive ribs 204 and the negative ribs 206 can have variable or a variety of rib spacings. Additionally, regardless of the values of the positive rib spacing SpacingPos or the negative rib spacing SpacingNeg, the total rib spacing SpacingRib can be fixed or variable.

[0079] As Figure 6A , 8, 9, the rib spacing dimensions SpacingRib, Spacing1Rib, Spacing2Rib, SpacingPos, Spacing1Pos, Spacing2Pos, SpacingNeg, Spacing1Neg, and Spacing2Neg are measured from the edge of one rib to the edge of the next rib, but can also be measured from center to center. Such measurements may be more accurate if the width of the ribs varies between different surfaces of the separator or on the same surface. In the selected exemplary embodiments, the positive rib spacing can be between about 1.0 mm and about 12 mm, preferably between about 2.0 mm and about 9.0 mm, and more preferably between about 4.0 mm and about 6.0 mm. In a particular exemplary embodiment, the negative rib spacing can be between about 1.0 mm and about 12 mm, preferably between about 2.0 mm and about 9.0 mm, and more preferably between about 4.0 mm and about 6.0 mm. In the selected embodiments, the positive rib spacing and the negative rib spacing can preferably be substantially equal to each other. The total rib spacing can generally be balanced, consistent, or fixed at a preferred value of 50% of the positive / negative rib spacing across the width of the separator. Thus, the negative ribs will be located midway between two positive ribs (but on the opposite surface of the positive ribs), while the positive ribs will be located midway between two negative ribs (but on the opposite surface of the negative ribs).

[0080] In some preferred exemplary embodiments, the backweb thickness can be between about 100 μm and about 300 μm, preferably between about 150 μm and about 250 μm, and more preferably between about 175 μm and about 225 μm.

[0081] In a particular preferred exemplary embodiment, the rib height can be between about 100 μm and about 600 μm, preferably between about 150 μm and about 500 μm, and more preferably between about 200 μm and about 400 μm. In the selected exemplary embodiments, the positive rib height and the negative rib height can be substantially equal to each other. Alternatively, the height of one set of ribs can be between about 100% and about 500% of the height of the other set of ribs, and preferably between about 100% and about 300%.

[0082] Although the rib spacing dimensions, backweb thickness dimensions, and rib height dimensions listed above are preferred for the selected embodiments, it should be understood that these dimensions can be outside of these ranges and still be within the scope of the present invention.

[0083] Reference Figure 10, an exemplary separator 300 of the present invention is provided with a generally flat back web 302, on which a set of main ribs 304 / 306 are provided and extend therefrom. Additionally, micro transverse ribs 305 / 307 can be provided on either or both sides of the separator back web 302 and between the main ribs 304 / 306. These micro ribs 305 / 307 provide stiffness along the cross-processing direction cmd and provide a method of reducing the weight / material of the separator 300. It should be understood that the naming of the reference numerals refers to the first plurality of main ribs 304 and the first set of micro transverse ribs 305 on the first surface of the separator back web 302, and the second plurality of main ribs 306 and the second set of micro transverse ribs 307 on the second surface of the separator back web 302. If provided on the surface facing the negative electrode, the micro transverse ribs 305 / 307 can be referred to as negative electrode transverse ribs.

[0084] Now refer to Figure 11 , an exemplary separator 400 of the present invention is provided with a generally flat back web 402, on which serrated ribs 404, 406 are provided and extend therefrom. The first plurality of serrated ribs 404 are provided on the first surface 102p, and the second plurality of serrated ribs 406 (depicted by dashed lines) are provided on the surface opposite to the first surface 402p. It can be seen that both sets of the plurality of serrated ribs 404, 406 are offset from each other, and the tips of the serrations are also offset from each other. The serrated ribs 404, 406 can also be or alternatively be stack ribs generally described in U.S. Patent No. 7,094,498 to Miller et al., which is incorporated herein by reference.

[0085] Now refer to Figure 12 , an exemplary separator 500 of the present invention is provided with a generally flat back web 502, on which protrusions 504, 506 are provided and extend therefrom. The first plurality of protrusions 504 are provided on the first surface 102p, and the second plurality of protrusions 506 (depicted by dashed lines) are provided on the surface opposite to the first surface 502p. It can be seen that both sets of the plurality of protrusions 504, 506 are offset from each other, and the tips of the protrusions are also offset from each other. The protrusions 504, 506 can also be or alternatively be textures or textured ribs generally described in U.S. Patent No. 9,461,291 to Miller et al., which is incorporated herein by reference.

[0086] As discussed herein, separators currently sold, offered for sale, and used in flooded lead acid batteries, particularly those operating or intended to operate in a partial state of charge, exhibit the squeezing and acid displacement described above, which ultimately results in inoperable batteries. Accordingly, there is a need for improved separators for flooded lead acid batteries, particularly those operating in a partial state of charge (e.g., those for start / stop vehicles, electric vehicles, light electric vehicles, hybrid vehicles, power harvesting inverters, and / or the like), which have improved acid accessibility at the electrodes in a partial state of charge.

[0087] In selected embodiments, a positive rib or a negative rib can generally be any one or a combination of the following: uninterrupted or continuous, serrated, discontinuous, discrete teeth or serrated ribs, discrete intermittent ribs, buttress projections and / or buttress ribs, linear, curved, wavy, angled, continuous or discontinuous serrated ribs and / or sinusoidal ribs, ribs extending generally longitudinally in the machine direction of the separator, ribs extending generally transversely across the machine direction of the separator, ribs extending generally crosswise across the machine direction of the separator, grooves, channels, textured areas, embossments, discrete projections, depressions, posts, micro-posts, porous, non-porous, micro-ribs, micro cross-ribs, acid mixing ribs, and combinations thereof.

[0088] In an exemplary selected embodiment, the acid mixing ribs can be on either or both of the positive rib or the negative rib and can be any form or combination defined by an angle that is neither parallel nor orthogonal to the edge of the separator. Further, the angle can vary in columns, rows, and / or discrete groups of ribs. An angled rib pattern can be potentially preferred. RipTide TM An acid mixing rib configuration, which can help reduce, eliminate, and / or mitigate acid stratification in a particular battery, and / or reverse the effects and / or state of acid stratification in a particular battery. Additionally, the angle can be defined relative to the machine direction of the porous membrane, and the angle can be between about greater than zero degrees (0°) and about less than 180 degrees (180°), and between about greater than 180 degrees (180°) and about less than 360 degrees (360°).

[0089] The ribs can extend uniformly across the width of the separator from lateral edge to lateral edge. This is referred to as a common configuration. Alternatively, the separator can have side panels adjacent to the lateral edges, with a rib pattern on the side panels different from that of the main ribs. Or, alternatively, the side panels can be flat. The side panels can assist in sealing one edge of the separator to another edge, as is done when encapsulating the separator, which will be discussed below.

[0090] The separator 100 can be configured as a single-piece leaf-shaped or multi-piece leaf-shaped leaf, wrapper, sleeve, or as an envelope or bag-shaped separator. An exemplary envelope separator can encapsulate the positive electrode (positive electrode encapsulating separator), which gives the separator two inner sides facing the encapsulated positive electrode and two outer sides facing the adjacent negative electrodes. Alternatively, another exemplary envelope separator can encapsulate the negative electrode (negative electrode encapsulating separator), which gives the separator two inner sides facing the encapsulated negative electrode and two outer sides facing the adjacent positive electrodes. In such an encapsulated separator, the bottom edge 103 can be a folded or sealed crease edge. Additionally, the lateral edges can be continuous or discontinuous sealed seam edges. The edges can be clamped, adhered, or sealed by gluing, heating, ultrasonic welding, and / or the like, or any combination thereof.

[0091] Certain exemplary separators can be processed into hybrid envelopes. A hybrid envelope can be provided by forming one or more slits or openings before, during, or after folding the separator sheet in half and sealing the edges of the separator sheet together to form an envelope. The length of the opening can be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the entire edge length. The length of the opening can be from 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the entire edge length. The hybrid envelope can have 1 - 5, 1 - 4, 2 - 4, 2 - 3, or 2 openings, which can be arranged uniformly or non-uniformly along the bottom edge length. Preferably, there are no openings at the envelope corners. The slit can be cut out after folding and sealing the separator to form an envelope, or the slit can be formed before molding the porous membrane into an envelope.

[0092] It should be understood that the exemplary embodiments of the separators of the present disclosure or the present invention can be configured such that the surfaces, positive electrode ribs, and the like described as facing the positive electrode can be used as the surfaces, negative electrode ribs, and the like facing the negative electrode. Accordingly, the exemplary embodiments of the separators of the present disclosure or the present invention can be configured such that the surfaces, negative electrode ribs, and the like described as facing the negative electrode can be used as the surfaces, positive electrode ribs, and the like facing the positive electrode. Additionally, positive electrode envelopes, positive electrode hybrid envelopes, positive electrode sleeves, positive electrode bags, and the like can also be used as negative electrode envelopes, negative electrode hybrid envelopes, negative electrode sleeves, negative electrode bags, and the like, and vice versa. Generally, the embodiments of the present invention related to the positive electrode side, object, or electrode can be replaced with those related to the negative electrode side, object, or electrode, and vice versa, without departing from the scope of the present invention.

[0093] In certain embodiments, an improved separator including a porous membrane and ribs can be made from: natural or synthetic base materials, processing plasticizers, fillers, one or more natural or synthetic rubbers or latexes, and one or more other additives and / or coatings and / or the like.

[0094] In certain embodiments, exemplary natural or synthetic substrate materials can include: polymers, thermoplastic polymers, phenolic resins, natural or synthetic rubbers, synthetic wood pulp, lignin, glass fibers, synthetic fibers, cellulose fibers, and combinations thereof. In certain preferred embodiments, the exemplary separator can comprise a thermoplastic polymer. Exemplary thermoplastic polymers can in principle include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. In certain preferred embodiments, the exemplary thermoplastic polymers can include vinyl compounds and polyolefins. In certain embodiments, the vinyl compound can include, for example, polyvinyl chloride (PVC). In certain preferred embodiments, the polyolefin can include, for example, polyethylene, polypropylene, ethylene-butene copolymers, and combinations thereof, but polyethylene is preferred. In certain embodiments, the exemplary natural or synthetic rubber can include, for example, latex, non-crosslinked or crosslinked rubbers, crumbs or ground rubbers, and combinations thereof.

[0095] In selected embodiments, the separator can preferably comprise a polyolefin, particularly polyethylene. Preferably, the polyethylene is high molecular weight polyethylene (HMWPE). Exemplary HMWPE can have a molecular weight of at least 600,000. Even more preferably, the polyethylene is ultra-high molecular weight polyethylene (UHMWPE). Exemplary UHMWPE can have a molecular weight of at least 1,000,000, particularly greater than 4,000,000 and most preferably 5,000,000 to 8,000,000, measured by viscometry and calculated using the Margolie equation. In addition, exemplary UHMWPE can have a standard load melt index of substantially zero (0) measured using a 2,160 g standard load as specified in ASTM D 1238 (Condition E). Moreover, exemplary UHMWPE can have a viscosity value of not less than 600 ml / g, preferably not less than 1,000 ml / g, more preferably not less than 2,000 ml / g, and most preferably not less than 3,000 ml / g, determined in a solution of 0.02 g of polyolefin dissolved in 100 g of decalin at 130 °C.

[0096] The new separator disclosed herein may comprise latex and / or rubber. As used herein, "rubber" will describe rubber, latex, natural rubber, synthetic rubber, crosslinked or non-crosslinked rubber, cured or uncured rubber, crumb or ground rubber, or mixtures thereof. Exemplary natural rubbers may include blends of one or more polyisoprenes, which are commercially available from different suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber may be crosslinked rubber or non-crosslinked rubber. In certain preferred embodiments, the rubber is non-crosslinked rubber. In certain embodiments, the rubber may be a blend of crosslinked and non-crosslinked rubber.

[0097] In certain embodiments, exemplary processing plasticizers may include processing oils, petroleum, paraffin-based mineral oils, mineral oils, and combinations thereof.

[0098] The separator may comprise a filler having a high structural morphology. Exemplary fillers may include: silica, dry-processed finely divided silica, precipitated silica, amorphous silica, highly friable silica, alumina, talc, fish meal, fish bone meal, carbon, carbon black, and the like, and combinations thereof. In certain preferred embodiments, the filler is one or more silicas. High structural morphology refers to an increased surface area. The filler may have a high surface area, for example, greater than about 100 m 2 / g, 110 m 2 / g, 120 m 2 / g, 130 m 2 / g, 140 m 2 / g, 150 m 2 / g, 160 m 2 / g, 170 m 2 / g, 180 m 2 / g, 190 m 2 / g, 200 m 2 / g, 210 m 2 / g, 220 m 2 / g, 230 m 2 / g, 240 m 2 / g or 250 m 2 / g. In some embodiments, the filler (e.g., silica) may have from about 100 m 2 / g to 300 m 2 / g, 125 m 2 / g to 275 m2 / g, 150 m 2 / g to 250 m 2 / g or preferably 170 m 2 / g to 220 m 2 / g of surface area. The surface area can be evaluated by obtaining the multi-point BET nitrogen surface area using TriStar 3000TM. The high structure morphology enables the filler to accommodate more oil during the manufacturing process. For example, a filler with a high structure morphology has a high level of oil absorption rate, such as greater than about 150 ml / 100 g, 175 ml / 100 g, 200 ml / 100 g, 225 ml / 100 g, 250 ml / 100 g, 275 ml / 100 g, 300 ml / 100 g, 325 ml / 100 g or 350 ml / 100 g. In some embodiments, the filler (such as silica) can have an oil absorption rate of about 200 ml / 100 g to 500 ml / 100 g, 200 ml / 100 g to 400 ml / 100 g, 225 ml / 100 g to 375 ml / 100 g, 225 ml / 100 g to 350 ml / 100 g, 225 ml / 100 g to 325 ml / 100 g, preferably 250 ml / 100 g to 300 ml / 100 g. In some cases, silica filler with an oil absorption rate of 266 ml / 100 g is used. This silica filler has a water content of 5.1%, a BET surface area of 178 m 2 / g, an average particle size of about 23 μm, a sieve residue value of about 0.1% on a 230-mesh screen, and a bulk density of about 135 g / L.

[0099] When forming an exemplary lead-acid battery separator of the type shown herein, silica having a relatively high level of oil absorption rate and a relatively high level of affinity for a plasticizer (such as mineral oil) is dispersed in a mixture of a polyolefin (such as polyethylene) and a plasticizer as desired. In the past, when a large amount of silica was used to manufacture such a separator or membrane, some separators suffered from poor dispersibility caused by silica aggregation. In at least certain of the inventive separators shown and described herein, since there are few silica aggregates or agglomerates inhibiting the molecular motion of the polyolefin when cooling the molten polyolefin, the polyolefin (such as polyethylene) forms a shish-kebab structure. All of these contribute to improving the ion permeability through the resulting separator membrane, and the formation of the shish-kebab structure or morphology means that a separator with mechanical strength maintained or even improved and a lower overall ER is produced.

[0100] In some selected embodiments, the filler (e.g., silica) has an average particle size of no greater than about 25 μm, and in some cases, no greater than about 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm. In some cases, the average particle size of the filler particles is from about 15 μm to about 25 μm. The particle size of the silica filler and / or the surface area of the silica filler contribute to the oil absorption of the silica filler. The silica particles in the final product or separator can fall within the sizes described above.

[0101] However, the initial silica used as a raw material can occur in the form of one or more agglomerates and / or aggregates and can have a size of about 200 μm or greater.

[0102] In some preferred embodiments, the silica used to manufacture the inventive separator has an increased number or amount of surface silanol groups (surface hydroxyl groups) compared to the silica fillers previously used to manufacture lead-acid battery separators. For example, the silica fillers that can be used in conjunction with the specific preferred embodiments herein can be those that have at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, or at least about 35% more silanol and / or hydroxyl surface groups than the known silica fillers used to manufacture known polyolefin lead-acid battery separators.

[0103] For example, the ratio of silanol groups (Si-OH) to silicon element (Si), (Si-OH) / Si, can be measured as follows.

[0104] 1. Freeze-crush a polyolefin porous membrane (wherein a specific inventive membrane contains a specific type of oil-absorbing silica according to the present invention) and prepare a powdered sample for solid-state nuclear magnetic resonance spectroscopy ( 29 Si-NMR).

[0105] 2. Perform 29 Si-NMR on the powdered sample and observe the spectrum, which includes the spectral intensity of Si directly bonded to a hydroxyl group (spectrum: Q2 and Q3) and the spectral intensity of Si directly bonded only to oxygen atoms (spectrum: Q4). The molecular structure of each NMR peak spectrum can be depicted as:

[0106] .Q2: (SiO)2-Si*-(OH)2: There are two hydroxyl groups

[0107] .Q3: (SiO)3-Si*-(OH): There is one hydroxyl group

[0108] .Q4: (SiO)4-Si*: All Si bonds are SiO

[0109] wherein, Si* is the element proven by NMR observation.

[0110] 3. For observation 29 The conditions for Si-NMR are as follows:

[0111] . Instrument: Bruker BioSpin Avance 500

[0112] . Resonance frequency: 99.36 MHz

[0113] . Sample amount: 250 mg

[0114] . NMR tube:

[0115] . Observation method: DD / MAS

[0116] . Pulse width: 45°

[0117] . Repetition time: 100 s

[0118] . Scans: 800

[0119] . Magic angle spinning: 5,000 Hz

[0120] . Chemical shift reference: For silicone rubber, -22.43 ppm

[0121] 4. Numerically, separate the peaks of the separated spectra and calculate the area ratio of each peak belonging to Q2, Q3, and Q4. Then, based on these ratios, calculate the molar ratio of the hydroxyl groups (-OH) directly bonded to Si. The conditions for numerical peak separation are carried out as follows:

[0122] . Fitting region: -80 to -130 ppm

[0123] . Initial peak tops: Respectively, for Q2: -93 ppm, Q3: -101 ppm, Q4: -111 ppm.

[0124] . Initial maximum half-widths: Respectively, for Q2: 400 Hz, Q3: 350 Hz, Q4: 450 Hz.

[0125] . Gaussian function ratio: Initially 80% and 70% to 100% during fitting.

[0126] 5. Calculate the peak area ratios of Q2, Q3, and Q4 (total is 100) based on each peak obtained by fitting. The NMR peak area corresponds to the number of molecules of each silicate bond structure (therefore, for the Q4 NMR peak, there are four Si-O-Si bonds within the silicate structure; for the Q3 NMR peak, there are three Si-O-Si bonds within the silicate structure and one Si-OH bond; for the Q2 NMR peak, there are two Si-O-Si bonds within the silicate structure and two Si-OH bonds). Thus, the number of each hydroxyl group (-OH) in Q2, Q3, and Q4 is multiplied by two (2), one (1), and zero (0), respectively. Add these three results. This sum value shows the molar ratio of the hydroxyl groups (-OH) directly bonded to Si.

[0127] In certain embodiments, the silica may have a molecular ratio of OH to Si groups measured by 29 Si-NMR, which may be in the range of about 21:100 to about 35:100; in some preferred embodiments, about 23:100 to about 31:100; in certain preferred embodiments, about 25:100 to about 29:100; in other preferred embodiments, at least about 27:100 or greater.

[0128] In some selected embodiments, using the fillers described above enables a greater proportion of processing oil to be used in the extrusion step. Since the porous structure in the separator is partly formed by removing the oil after extrusion, a higher initial oil absorption results in a higher porosity or a higher void volume. Since the processing oil is an essential component of the extrusion step, the oil is a non-conductive component of the separator. The residual oil in the separator protects the separator from oxidation when in contact with the positive electrode. In the production of conventional separators, the precise amount of oil in the processing step can be controlled. Generally, conventional separators use about 50 wt% to 70 wt% of processing oil, in some embodiments about 55 wt% to 65 wt%, in some embodiments about 60 wt% to 65 wt%, and in some embodiments about 62 wt%. It is known that reducing the oil below about 59% can cause combustion due to increased friction with the extruder components. However, increasing the oil far above the specified amount may cause shrinkage during the drying stage, resulting in dimensional instability. Although previous attempts to increase the oil content led to pore shrinkage or reduction during oil removal, the separators prepared as disclosed herein exhibit minimal shrinkage and reduction, if any, during oil removal. Thus, the porosity can be increased without sacrificing pore size and dimensional stability, thereby reducing the resistance.

[0129] In certain selected embodiments, the use of the filler described above can reduce the final oil concentration in the finished separator. Since oil is a non-conductor, reducing the oil content can increase the ionic conductivity of the separator and help reduce the ER of the separator. Therefore, a separator with a reduced final oil content can have improved efficiency. In certain selected embodiments, separators are provided having a final processed oil content (by weight) of less than 20%, such as between about 14% and 20%, and in some particular embodiments, less than about 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6% or 5%.

[0130] The filler can further reduce the so-called hydration spheres of electrolyte ions, enhancing their transmembrane transport and thus again reducing the total resistance or ER of the battery (such as an enhanced flooded battery) or system.

[0131] One or more fillers can comprise various substances (e.g., polar substances such as metals) that assist the flow of electrolyte and ions through the separator. When such a separator is used in a flooded battery (such as an enhanced flooded battery), this also results in a reduction in the total resistance.

[0132] In certain embodiments, the separator can comprise performance enhancing additives in the form of conductive components or nucleating additives and / or coatings. The conductive components or nucleating additives can preferably be stable in the battery electrolyte and can be further dispersed in the electrolyte.

[0133] Exemplary forms of the conductive components and / or coatings can be or comprise carbon, such as carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, oxidized carbon, and combinations thereof. In addition to these various forms of carbon, the nucleating additives and / or coatings can also include or comprise barium sulfate (BaSO4) alone or in combination with carbon. An exemplary form of carbon is -135. An exemplary preferred form of carbon is manufactured by Cabot Corporation of Boston, MA, USA -51. The inventors infer that the larger the surface area of the carbon, the greater the dynamic charge acceptance in the battery. For example, -51 has a specific surface area of at least about 1,300 m 2 / g to about 1,500 m 2 / g, while keitjen black has a specific surface area of at least about 1,250 m2 Surface area per g.

[0134] The nucleating coating can be applied to the final separator by means such as slurry coating, slot die coating, spraying, curtain coating, inkjet printing, screen printing, or by vacuum deposition or chemical vapor deposition (CVD). Additionally, the additive and / or coating can be provided as a woven or non-woven carbon paper and be disposed between and in intimate contact with the separator and the electrode.

[0135] The nucleating additive and / or coating can be within the separator or on one or both surfaces of the separator facing the electrodes. Generally, the coating or layer of the nucleating additive can be only on the surface facing the negative electrode. However, it can be on the surface facing the positive electrode or on both surfaces.

[0136] In certain embodiments, the nucleating additive can be added to the extrusion mixture of the base material and extruded together with the separator, or co-extruded as a layer on the separator. When included in the extrusion mixture, the nucleating additive can replace some of the silica filler in an amount of about 5% to about 75% by weight. For example, the nucleating additive can be about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or about 75% by weight. In other exemplary embodiments, the nucleating additive can be no greater than about 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10% or about 5% by weight.

[0137] In certain selected embodiments, the filler can be alumina, talc, silica or a combination thereof. In some embodiments, the filler can be precipitated silica, and in some embodiments, the precipitated silica can be amorphous silica. In some embodiments, it is preferred to use aggregates and / or agglomerates of silica, which enable the filler to be finely dispersed throughout the separator, thereby optimizing the curvature and reducing the resistance. In certain preferred embodiments, the filler (such as silica) is characterized by a high level of brittleness. Good brittleness improves the dispersion of the filler throughout the polymer during the extrusion process of the porous membrane, increases the porosity, and thus increases the total ionic conductivity through the separator.

[0138] Using a filler having one or more of the above properties enables the production of a separator with a higher final porosity. The separators disclosed herein can have a final porosity greater than about 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 75% or 80%. The porosity can be measured using the gas adsorption method. The porosity can be measured by BS-TE-2060.

[0139] In some selected embodiments, the porous separator may have a greater proportion of larger pores while maintaining an average pore size not greater than about 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm or 0.1 μm.

[0140] According to at least one embodiment, the separator is made by mixing polyethylene (such as UHMWPE) with processing oil and filler and any desired additives. According to at least one other embodiment, the separator is made by mixing UHMWPE with processing oil and talc. According to at least one other embodiment, the separator is made by mixing with UHMWPE processing oil and silica (such as precipitated silica, such as amorphous precipitated silica). Thereafter, the additives can be applied to the separator by one or more of the techniques described above.

[0141] In addition to reducing resistance and increasing cold start current, the preferred separator is also designed to provide other benefits. In terms of assembly, the separator is easier to pass through processing equipment, so manufacturing efficiency is higher. To prevent short circuits during high-speed assembly and in later use, compared with standard PE separators, the separator has excellent puncture strength and oxidation resistance. Combining reduced resistance and increased cold start current, battery manufacturers may find improved and sustained electrical performance when using these new separators in their batteries.

[0142] In a specific exemplary aspect, the separator may be provided with a carbon and / or nucleating additive layer or filler. The nucleating additive may be conductive and is one of carbon or barium sulfate (BaSO 4 ). Exemplary carbon additives may be carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, oxidized carbon and combinations thereof. The conductive component or nucleating additive may have a specific surface area of at least about 1,250 m 2 / g to about 1,750 m 2 / g or greater. The nucleating additive or conductive component may be an additive within the separator or an additive on the surface of the separator. The conductive component or nucleating additive can be applied to the surface of the separator, scrim and / or pad by the following methods: roll coating, chemical vapor deposition, coextrusion, controlled combustion of the surface to carbonize, controlled combustion of the surface to carbonize by plasma exposure, controlled combustion of the surface to carbonize by UV exposure, toner printing, inkjet printing, flexographic printing, lithographic printing, slurry coating, spraying an aqueous carbon suspension, impregnation and combinations thereof.

[0143] In certain embodiments, exemplary separators can include one or more performance enhancing additives added to the separator or the porous membrane. Performance enhancing additives can be surfactants, wetting agents, colorants, antistatic additives, antimony inhibiting additives, UV - protecting additives, antioxidants, and / or the like, and combinations thereof. In certain embodiments, the added surfactant can be an ionic, cationic, anionic, or non - ionic surfactant.

[0144] In certain embodiments described herein, a reduced amount of anionic or non - ionic surfactant is added to the inventive porous membrane or separator. Due to the lower amount of surfactant used, desired characteristics can include reduced total organic carbon (TOC) and / or reduced volatile organic compounds (VOC).

[0145] Certain suitable surfactants are non - ionic, and other suitable surfactants are anionic. The additive can be a single surfactant or a mixture of two or more surfactants, such as two or more anionic surfactants, two or more non - ionic surfactants, or at least one ionic surfactant and at least one non - ionic surfactant. Certain suitable surfactants can have an HLB value of less than 6, preferably less than 3. Using these particular suitable surfactants in combination with the inventive separators described herein can produce further improved separators that, when used in lead - acid batteries, result in reduced water consumption, reduced antimony poisoning, improved cycling, reduced floating current, reduced floating voltage, and / or the like, or any combination thereof, for the lead - acid battery. Suitable surfactants include surfactants such as alkyl sulfates, alkyl aryl sulfonates, alkylphenol - alkylene oxide adducts, soaps, alkylnaphthalene sulfonates, one or more sulfosuccinates, such as anionic sulfosuccinates, dialkyl esters of sulfosuccinates, amino compounds (primary, secondary, tertiary amines or quaternary amines), block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, and salts of mono - and dialkyl phosphates. Additives can include non - ionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and their mixtures, amine ethoxylates, ethoxylated sorbitan fatty acid esters, silicone - based surfactants, ethylene - vinyl acetate terpolymers, ethoxylated alkylaryl phosphates of fatty acids, and sucrose esters.

[0146] In certain embodiments, the additive can be represented by a compound of formula (I).

[0147]

[0148] Where:

[0149] . R is a linear or non-aromatic hydrocarbon group having 10 to 4200 carbon atoms, preferably 13 to 4200 carbon atoms, which may be interrupted by oxygen atoms;

[0150] . R 1 = H, or preferably H, where k = 1 or 2;

[0151] . M is an alkali metal or alkaline earth metal ion, H+, or where not all variables M are H+ simultaneously;

[0152] . n = 0 or 1;

[0153] . m = 0 or an integer from 10 to 1400; and

[0154] . x = 1 or 2.

[0155] In the compounds according to formula (I), the ratio of oxygen atoms to carbon atoms is in the range of 1:1.5 to 1:30, and m and n cannot be 0 simultaneously. However, preferably only one of the variables n and m is not equal to 0.

[0156] The so-called non-aromatic hydrocarbon group means a radical that does not contain an aromatic group or that itself represents an aromatic group. The hydrocarbon group may be interrupted by oxygen atoms (i.e., contains one or more ether groups).

[0157] R is preferably a straight-chain or branched aliphatic hydrocarbon group that may be interrupted by oxygen atoms. Saturated, non-crosslinked hydrocarbon groups are very particularly preferred. However, as described above, in certain embodiments, R may be aromatic-ring-containing.

[0158] By using the compounds according to formula (I) in the production of battery separators, the separators can be effectively protected against oxidative damage.

[0159] Battery separators containing the compounds according to formula (I) are preferred, where:

[0160] . R is a hydrocarbon group having 10 to 180, preferably 12 to 75, and very particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20, and more preferably 1 to 8 oxygen atoms, particularly preferably the hydrocarbon group of formula R 2 —[(OC2H4) p (OC3H6) q —, where:

[0161] . R2 is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, and particularly preferably 14 to 20 carbon atoms, where R2 may be linear or non-linear, such as containing an aromatic ring;

[0162] . P is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4; and

[0163] . q is an integer from 0 to 30, preferably from 0 to 10, particularly preferably from 0 to 4;

[0164] . Compounds in which the sum of p and q is from 0 to 10, in particular from 0 to 4, are particularly preferred;

[0165] . n = 1; and

[0166] . m = 0.

[0167] The formula R 2 —[(OC2H4) p (OC3H6) q —should be understood to also include those compounds in which the sequence of groups in the square brackets is different from that shown. For example, according to the invention, compounds in which the radicals in the brackets are formed by alternating (OC2H4) and (OC3H6) groups are suitable.

[0168] It has been confirmed that additives in which R 2 is a straight-chain or branched-chain alkyl group having 10 to 20, preferably 14 to 18 carbon atoms are particularly advantageous. OC2H4 preferably represents OCH2CH2, and OC3H6 represents OCH(CH3)2 and / or OCH2CH2CH3.

[0169] As preferred additives, mention may be made in particular of alcohols (p = q = 0; m = 0), primary alcohols being particularly preferred, fatty alcohol ethoxylates (p = 1 to 4, q = 0), fatty alcohol propoxylates (p = 0; q = 1 to 4) and fatty alcohol alkoxylates (p = 1 to 2; q = 1 to 4), and ethoxylates of primary alcohols being preferred. Fatty alcohol alkoxylates can be obtained, for example, by reacting the corresponding alcohols with ethylene oxide or propylene oxide.

[0170] It has been shown that additives of the m = 0 type that are insoluble or only sparingly soluble in water and sulfuric acid are particularly advantageous.

[0171] Also preferred are additives containing compounds according to formula (I), wherein:

[0172] . R is an alkyl group having 20 to 4200, preferably 50 to 750 and very particularly preferably 80 to 225 carbon atoms;

[0173] . M is an alkali metal or alkaline earth metal ion, H+ or in particular alkali metal ions such as Li + , Na + and K + or H + , where not all of the variables M are H at the same time+ ;

[0174] .n = 0;

[0175] .m is an integer from 10 to 1400; and

[0176] .x = 1 or 2.

[0177] In certain embodiments, suitable additives can include, in particular, polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers, wherein at least a portion of the acid groups, such as preferably 40% and particularly preferably 80%, are neutralized. The percentages refer to the number of acid groups. Very particularly preferred is poly(meth)acrylic acid present entirely in the form of a salt. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium (NR4, where R is hydrogen or a carbon functional group). Poly(meth)acrylic acid can include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acid is preferred, and in particular polyacrylic acid having an average molar mass Mw of from 1,000 g / mol to 100,000 g / mol, particularly preferably from 1,000 g / mol to 15,000 g / mol, and very particularly preferably from 1,000 g / mol to 4,000 g / mol. The molecular weight of poly(meth)acrylic acid polymers and copolymers is determined by measuring the viscosity (Fikentscher constant) of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution.

[0178] Also suitable are copolymers of (meth)acrylic acid, in particular copolymers containing, in addition to (meth)acrylic acid, ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and / or 2-ethylhexyl acrylate as comonomers. Copolymers containing at least 40 wt% and preferably at least 80 wt% of (meth)acrylic acid monomers are preferred, where the percentages are based on the monomer or the acid form of the polymer.

[0179] For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, in particular sodium hydroxide, are particularly suitable. Additionally, coatings and / or additives for reinforcing the separator can include, for example, metal alkoxides, where the metal can be, by way of example only (not intended to be limiting), Zn, Na, or Al, such as sodium ethoxide, by way of example only.

[0180] In some embodiments, the porous polyolefin porous membrane may include a coating on one or both sides of such a layer. Such a 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 No. 9,876,209 (incorporated herein by reference). Such a coating may, for example, reduce the overcharge voltage of the battery system, thereby extending battery life due to less grid corrosion and preventing drying out and / or water consumption.

[0181] In certain selected embodiments, the membrane can be prepared by combining about 5% to 15% by weight of a polymer (in some cases, about 10% of the polymer, such as polyethylene), about 10% to 75% of a filler (such as silica, in some cases, about 30% of the filler), and about 10% to 85% of a processing oil (in certain cases, about 60% of the processing oil). In other embodiments, the filler content is reduced while the oil content is higher, for example, greater than about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70% by weight. The filler:polymer ratio (by weight) can be about (or can be between approximately these specific ranges), such as 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, 5.5:1 or 6:1. The filler:polymer ratio (by weight) can be from about 1.5:1 to about 6:1, in some cases, from 2:1 to 6:1, from about 2:1 to 5:1, from about 2:1 to 4:1, and in some cases, from about 2:1 to about 3:1. The amounts of filler, oil, and polymer are all balanced for operability and the desired separator characteristics (such as resistance, basis weight, puncture resistance, bending stiffness, antioxidant resistance, porosity, physical strength, flatness, etc.).

[0182] According to at least one embodiment, the porous membrane may comprise UHMWPE mixed with a processing oil and precipitated silica. According to at least one embodiment, the porous membrane may comprise UHMWPE mixed with a processing oil, an additive, and precipitated silica. The mixture may also include small amounts of other additives or reagents common in the separator art (such as surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like and combinations thereof). In certain cases, the porous polymer layer can be a homogeneous mixture of about 8 vol% to about 100 vol% polyolefin, about 0 vol% to about 40 vol% plasticizer, and about 0 vol% to about 92 vol% inert filler material. The preferred plasticizer is petroleum. Since the plasticizer is the component that is most easily removed from the polymer - filler - plasticizer composition by solvent extraction and drying, it is useful in imparting porosity to the battery separator.

[0183] In certain embodiments, the porous membranes disclosed herein can comprise latex and / or rubber, which can be natural rubber, synthetic rubber, or a mixture thereof. Natural rubber can include blends of one or more polyisoprenes, which can be commercially available from different suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber can be crosslinked rubber or non-crosslinked rubber. In certain preferred embodiments, the rubber is non-crosslinked rubber. In certain embodiments, the rubber can be a blend of crosslinked and non-crosslinked rubber. The rubber can be present in the separator in an amount by weight of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or about 10% relative to the weight of the final separator (the weight of the polyolefin separator sheet or layer containing the rubber and / or latex). In certain embodiments, the rubber can be present in an amount of about 1 wt% to 6 wt%, about 3 wt% to 6 wt%, about 3 wt%, and about 6 wt%. The porous membrane can have a weight ratio of filler to polymer and rubber (filler: polymer and rubber) of about 2.6:1.0. The amounts of rubber, filler, oil, and polymer are balanced for operability and the desired separator characteristics such as electrical resistance, basis weight, puncture resistance, flexural stiffness, oxidation resistance, porosity, physical strength, flatness, etc.

[0184] The porous membranes containing polyethylene and filler (such as silica) manufactured according to the present invention generally have a residual oil content; in some embodiments, such residual oil content is from about 0.5% to about 40% of the total weight of the separator membrane (in some cases, from about 10 - 40% of the total weight of the separator membrane; in some cases, about 20% to 40% of the total weight). In certain selected embodiments herein, part to all of the residual oil content in the separator can be replaced by adding more performance enhancing additives such as surfactants, for example surfactants having a hydrophilic-lipophilic balance (HLB) of less than about 6, or for example non-ionic surfactants. For example, performance enhancing additives such as surfactants (such as non-ionic surfactants) can account for from 0.5% to up to all (for example, up to 20% or 30% or even 40%) of the residual oil content of the total weight of the porous separator membrane, thereby partially or fully replacing the residual oil in the separator membrane.

[0185] In some embodiments, an exemplary porous membrane can be prepared by mixing the components in an extruder. For example, about 5 wt% to 15 wt% of a polymer (e.g., polyethylene), about 10 wt% to 75 wt% of a filler (e.g., silica), about 10% to 85% of a processing oil, and optionally about 1 wt% to 50 wt% of a rubber and / or latex can be mixed in the extruder. The exemplary porous membrane can be manufactured by passing the components through a heated extruder, passing the extrudate produced by the extruder through a die and into a nip formed by two heated presses or calenders or rollers to form a continuous web. A substantial amount of the processing oil in the web can be extracted by using a solvent. Thereafter, the web can be dried and cut into strips of a predetermined width and then wound onto a roll. Additionally, the presses or calender rolls can be engraved with various groove patterns to impart ribs, grooves, textured areas, protrusions, and / or the like as described in detail herein. The amounts of rubber, filler, oil, and polymer are all balanced for operability and the desired separator characteristics such as electrical resistance, basis weight, puncture resistance, flexural stiffness, oxidation resistance, porosity, physical strength, flatness, etc.

[0186] In addition to, or as an alternative to, adding to the components in the extruder, in certain embodiments the rubber is combined with the porous membrane after extrusion. For example, the rubber can be coated on one or both sides, preferably on the side facing the negative electrode, with a liquid slurry containing rubber and / or latex, optionally silica and water, and then dried such that a thin film of this material is formed on the surface of the exemplary porous membrane. To improve the wettability of this layer, a wetting agent known to be used in lead acid batteries can be added to the slurry. In certain embodiments, the slurry can further contain one or more performance enhancing additives as described herein. After drying, a porous layer and / or thin film is formed on the separator surface that adheres well to the porous membrane and only negligibly increases the resistance, if at all. After adding the rubber, further compression can be carried out using a press or calender or roller. Other possible methods of applying rubber and / or latex are by dip coating, roll coating, spray coating, curtain coating, or any combination thereof, to coat the rubber and / or latex slurry onto one or more surfaces of the separator. These processes can occur before or after the processing oil is extracted, or before or after it is cut into strips.

[0187] Further embodiments of the present invention relate to depositing rubber onto the membrane by impregnation and drying.

[0188] In certain embodiments, performance enhancing additives or reagents (such as surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like, and any combination thereof) can be mixed with other components within an extruder. The porous membrane according to the present disclosure can then be extruded into a sheet or web shape in substantially the same manner as described above and made into a finished product.

[0189] In certain embodiments, in addition to being added to the extruder, or as an alternative to adding to the extruder, one or more additives can be applied to the separator porous membrane, for example, when the separator porous membrane is made (e.g., after a large amount of processing oil is extracted, and before or after rubber is introduced). According to certain preferred embodiments, an additive or a solution of the additive (such as an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for applying non-thermally stable additives and additives soluble in the solvent used for extracting the processing oil. Particularly suitable solvents for the additives according to the present invention are low molecular weight alcohols such as methanol and ethanol, and mixtures of these alcohols with water. The application can be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides. The application can also be carried out simultaneously in a solvent bath during the process of extracting the pore former (such as the processing oil). In certain selected embodiments, a portion of the performance enhancing additive (such as a surfactant coating) added to the extruder before manufacturing the separator, or the performance enhancing additive (or both) can combine with antimony in the battery system and can deactivate it, and / or form a compound with it and / or cause it to fall into the battery sludge and / or prevent its deposition on the negative electrode. Surfactants or additives can also be added to the electrolyte, glass mat, battery case, sticker, adhesive pad, and / or the like, or combinations thereof.

[0190] In certain embodiments, the additive (e.g., nonionic surfactant, anionic surfactant, or a mixture thereof) can be at least about 0.5 g / m 2 、1.0 g / m 2 、1.5 g / m 2 、2.0 g / m 2 、2.5 g / m 2 、3.0 g / m 2 、3.5 g / m 2 、4.0 g / m 2 、4.5 g / m 2 、5.0 g / m 2 、5.5 g / m 2 、6.0 g / m 2 、6.5 g / m 2 、7.0 g / m 2 、7.5 g / m 2 、8.0 g / m 2, 8.5 g / m 2 , 9.0 g / m 2 , 9.5 g / m 2 or 10.0 g / m 2 or even up to about 25.0 g / m 2 The density or addition amount exists. The additive can be in an amount of about 0.5 - 15 g / m 2 , 0.5 - 10 g / m 2 , 1.0 - 10.0 g / m 2 , 1.5 - 10.0 g / m 2 , 2.0 - 10.0 g / m 2 , 2.5 - 10.0 g / m 2 , 3.0 - 10.0 g / m 2 , 3.5 - 10.0 g / m 2 , 4.0 - 10.0 g / m 2 , 4.5 - 10.0 g / m 2 , 5.0 - 10.0 g / m 2 , 5.5 - 10.0 g / m 2 , 6.0 - 10.0 g / m 2 , 6.5 - 10.0 g / m 2 , 7.0 - 10.0 g / m 2 , 7.5 - 10.0 g / m 2 , 4.5 - 7.5 g / m 2 , 5.0 - 10.5 g / m 2 , 5.0 - 11.0 g / m 2 , 5.0 - 12.0 g / m 2 , 5.0 - 15.0 g / m 2 , 5.0 - 16.0 g / m 2 , 5.0 - 17.0 g / m 2 , 5.0 - 18.0 g / m 2 , 5.0 - 19.0 g / m 2 , 5.0 - 20.0 g / m 2 , 5.0 - 21.0 g / m 2 , 5.0 - 22.0 g / m 2 , 5.0 - 23.0 g / m 2 , 5.0 - 24.0 g / m 2 or 5.0 - 25.0 g / m 2 The density or addition amount between these values exists on the separator.

[0191] Application can also be carried out by impregnating the battery separator in an additive or additive solution (solvent bath addition) and removing the solvent if necessary (e.g., by drying). In this way, the application of the additive can be combined with extraction, which is often used, for example, in the process of membrane production. Other preferred methods are spraying the surface with the additive, dip coating, roll coating or curtain coating one or more additives on the surface of the separator.

[0192] In a specific embodiment described herein, a reduced amount of ionic, cationic, anionic or non-ionic surfactant is added to the inventive separator. In this case, the desired characteristics may include reduced total organic carbon and / or reduced volatile organic compounds (due to the smaller amount of surfactant), and according to this embodiment, the desired inventive separator can be produced.

[0193] In a specific embodiment, an exemplary separator according to the present disclosure can be combined (laminated or otherwise) with another layer, such as a fibrous layer or fibrous mat having enhanced wicking properties and / or enhanced electrolyte wetting or retention properties. The fibrous mat can be woven, non-woven, flannel, mesh, net-like, single-layer, multi-layer (where each layer can have the same, similar or different characteristics as the other layers), made of glass fiber or synthetic fiber, a flannel made of synthetic fiber or a mixture of glass fiber and synthetic fiber, paper or a combination thereof.

[0194] In a specific embodiment, the fibrous mat (laminated or otherwise) can be used as a carrier for the additive material. The additive material can include, for example, rubber and / or latex, optional silica, water and / or one or more performance enhancing additives, such as the various additives described herein, or any combination thereof. For example, the additive material can be provided in the form of a slurry and then coated on one or more surfaces of the fibrous mat to form a film, or immersed and impregnated into the fibrous mat.

[0195] When there is a fibrous layer, it is preferred that the porous membrane has a larger surface area than the fibrous layer. In this way, when the porous membrane and the fibrous layer are combined, the fibrous layer does not completely cover the porous layer. Preferably, at least two opposite edge regions of the membrane layer remain uncovered to provide edges for heat sealing, which is beneficial for optionally forming bags or envelopes and / or the like. 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, and so on. The subsequently laminated separator can be cut into sheets. In certain embodiments, the fibrous mat is laminated to the ribbed surface of the porous membrane. In certain embodiments, the improved separator described herein provides advantages in processing and / or assembly for battery manufacturers because it can be supplied in the form of a roll and / or in the form of cut pieces. And as previously described, the improved separator can be a separate separator sheet or layer without adding one or more fibrous mats or the like.

[0196] If the fibrous mat is laminated to the porous membrane, the fibrous mat and the porous membrane can be adhered together by adhesion, heating, ultrasonic welding, extrusion, and / or the like or any combination thereof. Examples

[0197] Three sample separators were fabricated according to the description of the exemplary embodiments of the present invention detailed herein and tested against a control separator. Table 1 below describes the specifications of the four tested separators. As a proof of concept, the four separators were tested at 4 different pressures. The testing method used weights of 0.0 oz (ounce, 0.0 g), 8 oz (224 g), 11 oz (308 g), and 16 oz (448 g). These weights were applied to a circular plate with an area of 3.14 in 2 or 0.00203 m 2 Thus, based on the applied weight and the test area, the total applied force and pressure can be easily calculated. The applied forces were 0.0 N, 2.2 N, 3.0 N, and 4.4 N. The pressures used were 0.0 kPa (no force applied), 1.098 kPa (applied force of 2.2 N), 1.510 kPa (applied force of 3.0 N), and 2.196 kPa (applied force of 4.4 N). The plate used during the testing applied a small amount of weight (due to its mass), so the actual applied pressure may be slightly larger than the listed pressure, but it can be ignored.

[0198]

[0199] Table 1 Separator Characteristics and Specifications

[0200] Five samples of each test septum were tested at four different pressures and the average total thickness was calculated, as shown in Tables 2 to 6 below. The total thickness was measured at a pressure of 0.0 kPa (i.e., no pressure). This measurement is the relaxed thickness of the septum. All other measurements of the sample under pressure represent the total thickness in the compressed state.

[0201] Total thickness of Sample A (mm)

[0202]

[0203] Table 2

[0204] Total thickness of Sample B (mm)

[0205]

[0206] Table 3

[0207] Total thickness of Sample C (mm)

[0208]

[0209] Table 4

[0210] Total thickness of Sample D (mm)

[0211]

[0212] Table 5

[0213] Total thickness of control sample (mm)

[0214]

[0215] Table 6

[0216] Now refer to Figure 13 , which depicts graphically the average total thickness of the four test septa. Figure 13 The data described in

[0217] Average total thickness (mm)

[0218]

[0219] Table 7

[0220] Now refer to Figure 14 and Figure 15 , which depicts graphically the percentage change in thickness of the four test septa from the relaxed state. Figure 14 The data described in Figure 15 is shown in Table 8 below,

[0221] Change in thickness from previous state (μm)

[0222]

[0223] Table 8

[0224] Percentage change in thickness from the relaxed state (%)

[0225]

[0226] Table 9

[0227] As shown, the reference separator maintains a substantially constant total thickness under all applied pressures. As shown in Tables 8 and 9 above, separator samples A and B made of polyethylene show significant changes in the total thickness percentage during the entire compression. However, Table 8 above shows that most of the changes occur in the first stage of compression. Considering the overall change, the compression of sample B is twice that of sample A (total change: -220 μm vs. -110 μm). Phenolic-based separator samples C and D have the same backsheet thickness and the same rib spacing. The difference lies in the rib height. As shown in Table 8, the two samples have similar compression values (total change: -200 μm vs. -210 μm), and the total thickness reduction between the two samples only differs by 10 μm. Compared with sample B, the phenolic separators (samples C and D) seem to be more constant in compression during the entire compression step. Table 8 also shows that when the negative and positive rib spacings increase from approximately 4 mm in sample A to approximately 6 mm in sample B, the compressibility (total change) doubles. Therefore, it seems that a spacing greater than approximately 4 mm is important for achieving higher compressibility.

[0228] In addition, it was found that the separators described herein exhibit excellent recoverability after the application of pressure.

[0229] The written description of the above structures and methods is for illustrative purposes only. The examples are used to disclose exemplary embodiments, including the best mode, and also enable any person skilled in the art to practice the invention, including making and using any device or system and performing any included method. 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 can be combined in any combination. The steps of the methods described herein can be performed in any physically possible order. The patentable scope of the invention is defined by the appended claims and may include other embodiments that occur to those skilled in the art. If such other embodiments have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that do not differ materially from the literal language of the claims, they are intended to be within the scope of the claims.

[0230] The present invention may be embodied in other forms without departing from the spirit and essential attributes thereof. Accordingly, when indicating the scope of the present invention, reference should be made to the appended claims rather than the foregoing specification. What is disclosed are components that can be used to implement the disclosed methods and systems. These and other components are disclosed herein, and it should be understood that while specific references to every different individual and collective combination and permutation may not be explicitly disclosed, for all methods and systems, each and every one is herein specifically contemplated and described. This applies to all aspects of this application, including but not limited to the steps in the disclosed methods. Thus, if there are multiple additional steps that can be performed, it should be understood that each of these additional steps can be performed in conjunction with any specific implementation or combination of implementations of the disclosed methods.

[0231] For at least certain applications or cells, details of one or more exemplary embodiments, aspects, or objects of the present invention provide a battery separator having a variable total thickness, such as a total thickness that varies as a function of the pressure applied to the separator. Other features, objects, and advantages of the present invention provide reduced battery failures, increased battery cycle life, and / or improved performance. More particularly, there remains a need to provide such a separator that can accommodate a varying electrode spacing during at least one of the manufacturing process of the battery and / or during its use after it has been manufactured.

[0232] In the detailed description of the invention and the claims set forth below are details of one or more exemplary embodiments, aspects, or objects. From the detailed description of the invention and the claims set forth below, other features, objects, and advantages will be apparent. In accordance with one or more selected embodiments, aspects, or objects, the present disclosure or invention at least addresses the difficulties, problems, or needs enumerated herein, and in some cases, provides solutions that are surprisingly and unexpectedly beyond the needs and expectations.

[0233] In accordance with at least certain exemplary embodiments, objects, or aspects, the present disclosure or invention can provide new or improved separators, battery cells, batteries, systems that at least overcome the above problems, methods of manufacturing, using, and / or applying such new or improved separators, battery cells, batteries, and / or systems. For example, at least certain exemplary embodiments, objects, or aspects provide a battery having a separator that can accommodate electrodes having a varying spacing, and a battery having a separator with a variable thickness.

[0234] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention provides a separator, the composition, physical properties, and characteristics of which are synergistically combined to address previously unmet needs in the lead-acid battery industry in a surprising and unexpected manner through an improved battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a battery using the separator as described herein, which addresses previously unmet needs in the lead-acid battery industry in a surprising and unexpected manner through an improved lead-acid battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a system using the battery as described herein, which addresses previously unmet needs in the lead-acid battery industry in a surprising and unexpected manner by using an improved system (which uses the lead-acid battery as described herein, and the lead-acid battery uses the invented separator as described herein).

[0235] According to at least certain embodiments, the present disclosure or invention is directed to new or improved separators, battery cells, batteries, systems, and / or methods of manufacturing and / or using and / or applying such new separators, battery cells, batteries, and / or systems. According to at least certain embodiments, the present disclosure or invention is directed to new or improved battery separators for use in: lead-acid batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, flat plate batteries, tubular batteries, deep cycle batteries, batteries operating in a partial state of charge (PSoC), valve-regulated lead-acid (VRLA) batteries, gel batteries, absorbed glass mat (AGM) batteries, inverter batteries, stationary batteries, batteries used during motion, energy storage devices for power generation (such as through steam turbine generators, such as in coal-fired and / or gas-fired power plants and / or nuclear power plants), energy storage devices for power generation through solar, wind, hydro, or other alternative and / or renewable energy sources, general energy storage batteries, uninterruptible power supply (UPS) batteries, batteries with high cold cranking amps (CCA) requirements, vehicle batteries (such as starting-lighting-ignition (SLI) vehicle batteries, idle start-stop (ISS) vehicle batteries), marine batteries, automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, forklift truck batteries, golf cart (also known as golf car) batteries, hybrid electric vehicle (HEV) batteries, electric vehicle batteries, light electric vehicle batteries, neighborhood electric vehicle (NEV) batteries, electric rickshaw batteries, electric tricycle batteries, electric bicycle batteries, electric scooter batteries, and / or the like and / or combinations thereof. According to selected embodiments, the present disclosure or invention is directed to battery separators for use in systems or vehicles containing the batteries mentioned above. According to at least certain aspects, the present disclosure or invention is directed to improved methods for manufacturing and / or using such improved separators, battery cells, batteries, systems, and / or the like.

[0236] According to a first selected embodiment of the present invention, the battery separator is provided with a porous membrane backing net having a first surface and a second surface, the second surface being on a side opposite to the first surface. The separator is further provided with a rib array composed of a first plurality of ribs extending from the first surface and a second plurality of ribs extending from the second surface. At least a portion of the first rib array is not disposed opposite to any of the second plurality of ribs disposed on the second surface.

[0237] According to some exemplary aspects of the present invention, the rib arrays may or may not be equally spaced apart. Additionally, either or both of the first plurality of ribs and the second plurality of ribs may or may not be equally spaced apart. These rib spacings may exist in any combination.

[0238] According to at least one aspect of the present invention, the rib array may be arranged such that one or more of the first plurality of ribs alternate with one or more of the second plurality of ribs across the width of the separator.

[0239] In some aspects, the separator may have micro ribs disposed on one or both surfaces of the separator. These micro ribs may be arranged between the first and second plurality of ribs in the processing direction of the separator or across the processing direction of the separator. The micro ribs may have a height of approximately 25 μm to approximately 75 μm.

[0240] In a selected embodiment, the first plurality of ribs may be substantially parallel to each other, the second plurality of ribs may be substantially parallel to each other, and / or the first plurality of ribs may be substantially parallel to the second plurality of ribs. The first plurality of ribs and the second plurality of ribs may be substantially parallel to the processing direction of the separator.

[0241] In a selected preferred aspect of the present invention, the first plurality of ribs and / or the second plurality of ribs may be spaced apart by the following distances: between approximately 4 mm and approximately 18 mm, between approximately 5 mm and approximately 16 mm, or between approximately 6 mm and approximately 14 mm. The spacing may be 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 11 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm, or 20 mm.

[0242] The results herein show that when using a spacing of approximately 6 mm (compared to 4 mm), the compressibility is significantly improved; and when the spacing exceeds 12 mm or 14 mm, such as 18 mm, 20 mm or greater, the compressibility decreases or disappears. At such higher spacings, acid displacement problems may occur.

[0243] According to a specific preferred embodiment of the present invention, the battery separator may have a relaxed state (wherein the porous membrane backing net is generally flat) and a compressed state different from the relaxed state (wherein the porous membrane backing net is generally warped).

[0244] According to a selected preferred embodiment, the separator has a total thickness defined by the distance between a plane formed by the tips of a first plurality of ribs and a plane formed by the tips of a second plurality of ribs. In the selected embodiment, the total thickness in the compressed state is at least about 500 μm. In the selected embodiment, the total thickness in the compressed state does not exceed about 2.0 mm. In other embodiments, the total thickness in the relaxed state does not exceed about 3.0 mm.

[0245] In the relaxed state, the total thickness can be measured as the sum of the thickness of the porous membrane backing mesh, the height of the first plurality of ribs, and the height of the second plurality of ribs. In this case, the total thickness in the relaxed state does not exceed about 3.0 mm.

[0246] In a particular exemplary embodiment, the first plurality of ribs have a first rib height of from about 200 μm to about 1.5 mm. Additionally, the second plurality of ribs have a second rib height of from about 200 μm to about 1.5 mm.

[0247] In some preferred embodiments, the first plurality of ribs have a first rib height and the second plurality of ribs include a second rib height. The first rib height is equal to from about 25% to about 400% of the second rib height.

[0248] Another aspect of the present invention provides a porous membrane backing mesh having a thickness between about 125 μm and about 250 μm.

[0249] In yet another aspect of the present invention, the battery separator can have a composition that includes at least one of the following: polymers, thermoplastic polymers, polyvinyl chloride (PVC), phenolic resins, natural or synthetic rubbers, synthetic wood pulp, lignin, glass fibers, synthetic fibers, cellulose fibers, and / or combinations thereof. The natural or synthetic rubbers can include one or more of the following: rubber, latex, natural rubber, synthetic rubber, crosslinked or non-crosslinked natural or synthetic rubbers, vulcanized or unvulcanized rubbers, shredded or ground rubbers, polyisoprene, methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers (such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber) and / or combinations thereof.

[0250] In some aspects of the present invention, the battery separator may further have a filler, which is at least one of the following: silica, dry-process finely divided silica, precipitated silica, amorphous silica, highly brittle silica, alumina, talc powder, fish meal, fish bone meal, barium sulfate (BaSO4), carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide and / or combinations thereof.

[0251] In other aspects of the present invention, the battery separator may further have a coating, which is at least one of the following: barium sulfate (BaSO4), carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide and / or combinations thereof.

[0252] In yet another exemplary aspect of the present invention, one or both of the first plurality of ribs and the second plurality of ribs are at least one of the following: uninterrupted ribs, discrete interrupted ribs, continuous ribs, discontinuous ribs, angled ribs, linear ribs, longitudinal ribs extending substantially in the processing direction of the porous membrane, transverse ribs extending substantially in the cross-processing direction of the porous membrane, cross-cut ribs extending substantially in the cross-processing direction of the porous membrane, cross ribs extending substantially in the cross-processing direction of the porous membrane, discrete teeth or toothed ribs, serrated, serrated ribs, stacked or ribbed ribs, curved or sinusoidal ribs, arranged in an uninterrupted or interrupted zigzag pattern, grooves, channels, textured areas, bumps, pillars, embossments, pits, porous, non-porous, micro ribs or micro cross ribs and combinations thereof. In another aspect, the exemplary battery separator may have a negative cross rib.

[0253] In a selected preferred embodiment of the present invention, the lead acid battery is provided with one or more positive electrodes and one or more negative electrodes, and an embodiment of the battery separator as generally described and claimed herein disposed therebetween.

[0254] In certain aspects of the present invention, the lead-acid battery can be one of the following: flooded lead-acid battery, enhanced flooded lead-acid battery (EFB), flat plate battery, tubular battery, deep cycle battery, battery operating in a partial state of charge (PSoC), valve-regulated lead-acid (VRLA) battery, gel battery, absorbent glass mat (AGM) battery, inverter battery, stationary battery, battery used during motion, energy storage battery for power generation, general energy storage battery, uninterruptible power supply (UPS) battery, battery with high cold cranking current (CCA) requirements, vehicle battery (such as starting-lighting-ignition (SLI) vehicle battery, idle start-stop (ISS) vehicle battery), marine battery, automotive battery, truck battery, motorcycle battery, all-terrain vehicle battery, forklift battery, golf cart (also known as golf car) battery, hybrid electric vehicle (HEV) battery, electric vehicle battery, light electric vehicle battery, neighborhood electric vehicle (NEV) battery, electric rickshaw battery, electric tricycle battery, electric bicycle battery, electric scooter battery, and / or the like and / or combinations thereof.

[0255] In certain preferred exemplary embodiments, the present invention can provide a vehicle, device, or system that uses a lead-acid battery as generally described and claimed herein, and the lead-acid battery uses a battery separator as generally described and claimed herein. The vehicle, device, or system can be at least one of the following: a power generation system (such as a steam turbine generator, such as a power plant using coal and / or gas, and / or a nuclear power plant), a power generation system generating electricity through solar energy, wind energy, hydropower, or other alternative and / or renewable energy sources, an uninterruptible power supply (UPS), a vessel, an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart (also known as golf car), a hybrid electric vehicle (HEV), an electric vehicle, a light electric vehicle, a neighborhood electric vehicle (NEV), an electric rickshaw, an electric tricycle, an electric bicycle, an electric scooter, and / or the like and / or combinations thereof.

[0256] In addition, a fiber mat can be provided. The mat can be one of the following: fiberglass, synthetic fiber, silica, at least one performance enhancing additive, latex, natural rubber, synthetic rubber, and combinations thereof, and can be non-woven, woven, mesh, flannelette, netting, and combinations thereof.

[0257] In addition, the battery separator can be provided as slices, leaves, bags, sleeves, wrappers, envelopes, and hybrid envelopes with an opening at the bottom.

[0258] A first plurality of ribs may be further provided to enhance acid mixing in the battery, particularly during battery movement. The separator may be arranged such that the first surface and the second surface are parallel to the direction in which the battery starts and stops moving. The separator may be provided with pads adjacent to the positive electrode, the negative electrode, or the separator. The pads may be made at least in part of: fiberglass, synthetic fibers, silica, at least one performance enhancing additive, latex, natural rubber, synthetic rubber, and any combination thereof. The pads may be non-woven, woven, mesh, flannel, reticulated, and combinations thereof.

[0259] In certain embodiments, the battery may operate at a depth of discharge between about 1% and about 99%.

[0260] In accordance with at least selected exemplary embodiments, aspects, or objectives, the present invention at least solves, meets, and / or overcomes difficulties, needs, and / or problems that have heretofore not been solved, met, and / or overcome by the current state of the art. In accordance with at least specific objectives, the present invention provides an improved separator, an improved battery using the improved separator, and / or an improved system using the improved battery, which at least overcome and in some cases surprisingly and unexpectedly overcome at least the above problems. The compositions and methods of the appended claims are not limited to the specific compositions and methods described herein (which are intended as illustrations of several aspects of the claims). Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various variations of the compositions and methods, in addition to those shown and described herein, are intended to fall within the scope of the appended claims. Further, although only specific representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps, even if not specifically recited, are intended to fall within the scope of the appended claims. Thus, combinations of steps, elements, components, or ingredients may be explicitly or less explicitly mentioned herein, but other combinations of steps, elements, components, and ingredients are included even if not explicitly stated. Except as in the examples or otherwise specified, all numbers expressing quantities of ingredients, reaction conditions, etc. used in the specification and claims should at least be understood as not being intended to limit the application of the doctrine of equivalents to the scope of the claims, and are to be interpreted in accordance with the number of significant figures and the ordinary rounding method. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention pertains. Publications cited herein and the materials cited therein are specifically incorporated by reference.

[0261] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that each of the endpoints of each range is significant with respect to the other endpoint and independent of the other endpoint. "Optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0262] Throughout the specification and claims of this specification, the word "comprising" and variations of the word, such as the present participle and third person singular form thereof, 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 for more specific embodiments of the invention and are also disclosed. "Exemplary" or "for example" means "an example" and is not intended to convey a preferred or ideal embodiment. Likewise, "such as" is not restrictive but is for explanatory or illustrative purposes.

[0263] In addition, the inventions illustratively disclosed herein may be suitably practiced in the absence of any element not specifically disclosed herein.

Claims

1. A battery separator, comprising: A porous membrane backing net, which includes a first surface and a second surface on the opposite side of the first surface; At least one rib array, which includes a first plurality of ribs extending from the first surface and a second plurality of ribs extending from the second surface; When assembled by a battery manufacturer, the first plurality of ribs are completely staggered from any of the second plurality of ribs provided on the second surface, and their vertical projections on the porous membrane backing net do not coincide; The porous membrane backing net is generally planar in the relaxed state during battery manufacturing; while in the compressed state adapting to the changing spacing between electrodes during battery use, it is generally warped, A first plane is formed by the tips of each of the first plurality of ribs; A second plane is formed by the tips of each of the second plurality of ribs; the total thickness is at least 500 μm in the compressed state, which is the distance between the first plane and the second plane.

2. The battery separator according to claim 1, wherein, The rib arrays are spaced apart at equal intervals.

3. The battery separator according to claim 1, wherein, The rib arrays are not spaced apart at equal intervals.

4. The battery separator according to claim 3, wherein The first plurality of ribs are spaced apart at equal intervals.

5. The battery separator according to claim 4, wherein, The second plurality of ribs are not spaced apart at equal intervals.

6. The battery separator according to claim 3, wherein, The second plurality of ribs are spaced apart at equal intervals.

7. The battery separator according to claim 6, wherein, The first plurality of ribs are spaced apart at equal intervals.

8. The battery separator according to claim 3, wherein The first plurality of ribs are not spaced apart at equal intervals, and the second plurality of ribs are not spaced apart at equal intervals.

9. The battery separator according to claim 1, wherein, The first plurality of ribs are spaced apart at a first distance; the second plurality of ribs are spaced apart at a second distance.

10. The battery separator according to claim 9, wherein, The first distance is equal to the second distance.

11. The battery separator according to claim 10, wherein, The rib arrays are spaced apart at equal intervals.

12. The battery separator according to claim 1, wherein, The rib array includes one or more ribs of the first plurality of ribs alternating with one or more ribs of the second plurality of ribs; and / or The first plurality of ribs and / or the second plurality of ribs are spaced apart at a distance between 4 mm and 18 mm.

13. The battery separator according to claim 1, further comprising micro cross ribs provided on the first surface, the second surface, or both the first surface and the second surface.

14. The battery separator according to claim 13, wherein, The micro cross ribs have a height between 25 μm and 75 μm.

15. The battery separator according to claim 1, wherein, Each of the first plurality of ribs is substantially parallel to each other.

16. The battery separator according to claim 15, wherein, Each of the second plurality of ribs is substantially parallel to each other.

17. The battery separator according to claim 16, wherein, The first plurality of ribs are substantially parallel to the second plurality of ribs.

18. The battery separator according to claim 17, wherein, The first plurality of ribs are substantially parallel to the processing direction of the separator.

19. The battery separator according to claim 12, wherein, The first plurality of ribs and / or the second plurality of ribs are spaced apart at a distance between 5 mm and 16 mm.

20. The battery separator according to claim 19, wherein, The first plurality of ribs and / or the second plurality of ribs are spaced apart at a distance between 6 mm and 14 mm.

21. The battery separator according to claim 1, wherein, The first plurality of ribs have a first rib height of 200 μm to 1.5 mm.

22. The battery separator according to claim 1, wherein, The second plurality of ribs have a second rib height of 200 μm to 1.5 mm.

23. The battery separator according to claim 1, wherein, The first plurality of ribs have a first rib height, and the second plurality of ribs have a second rib height; the first rib height is 25% to 400% of the second rib height.

24. The battery separator according to claim 1, wherein, The thickness of the porous membrane backing net is between 125 μm and 250 μm.

25. The battery separator according to claim 1, wherein, The battery separator further comprises one selected from the following: polyvinyl chloride, phenolic resin, natural or synthetic rubber, synthetic wood pulp, lignin, glass fiber, synthetic fiber, cellulose fiber, and combinations thereof.

26. The battery separator according to claim 25, wherein, The natural rubber or synthetic rubber includes one selected from the following: latex, crosslinked or uncrosslinked natural or synthetic rubber, cured or uncured rubber, rubber debris or rubber powder, polyisoprene, methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, brominated butyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber, and ethylene / vinyl acetate rubber, and combinations thereof.

27. The battery separator according to claim 1, wherein, The battery separator further includes a filler, which is at least one selected from the following: dry divided silica, precipitated silica, amorphous silica, highly brittle silica, alumina, talcum powder, fish meal, fish bone meal, barium sulfate, artificial graphite, activated carbon, carbon paper, acetylene black, high surface area carbon black, graphene, Ketjen black, carbon fiber, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide, and combinations thereof.

28. The battery separator according to claim 1, wherein, The battery separator further includes a coating, which is at least one selected from the following: barium sulfate, artificial graphite, activated carbon, carbon paper, acetylene black, high surface area carbon black, graphene, Ketjen black, carbon fiber, carbon nanotube, open-cell carbon foam, carbon pad, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, flake graphite, carbon monoxide, and combinations thereof.

29. The battery separator according to claim 1, wherein, The first plurality of ribs and / or the second plurality of ribs are selected from: linear solid ribs, serrated or zigzag ribs, stacked or ribbed ribs, sinusoidal ribs, solid or discontinuous zigzag ribs formed, embossing, pits, micro ribs, protrusions.

30. The battery separator according to claim 1, further comprising a negative side transverse rib, or further comprising an acid mixing rib.

31. The battery separator according to claim 27 or 28, wherein, The graphene is high surface area graphene.

32. The battery separator according to claim 1, having a variable total thickness that can adapt to changes in the electrode spacing, wherein, Its porous membrane backsheet is generally planar in the relaxed state; while in the compressed state adapting to the varying spacing between electrodes, it is generally warped; all negative electrodes are located in the middle of two positive electrodes, and all positive electrodes are located in the middle of two negative electrodes.

33. The battery separator according to claim 1, which is a compressible battery separator and has the ability to adapt to the varying spacing between electrodes in a lead-acid battery, wherein, Its porous membrane backsheet is generally planar in the relaxed state; while in the compressed state adapting to the varying spacing between electrodes, it is generally warped, all negative electrodes are located in the middle of two positive electrodes, and all positive electrodes are located in the middle of two negative electrodes.

34. The battery separator according to claim 1, which is a thickness-compressible battery separator, wherein, All negative electrodes are located in the middle of two positive electrodes, and all positive electrodes are located in the middle of two negative electrodes; the battery separator has the ability to change its thickness by at least 12% from the relaxed state to the compressed state.

35. A variable-thickness battery separator capable of adapting to changes in electrode spacing, comprising: A porous membrane backsheet, which includes a first surface and a second surface on the opposite side of the first surface; At least one rib array, which includes a first plurality of ribs extending from the first surface and a second plurality of ribs extending from the second surface; During the battery assembly process, the first plurality of ribs are completely staggered from any of the second plurality of ribs provided on the second surface, and their vertical projections on the porous membrane backsheet do not overlap; All the negative electrode ribs are located in the middle of two positive electrode ribs, and all the positive electrode ribs are located in the middle of two negative electrode ribs; The porous film back net is generally planar in the relaxed state during battery manufacturing; while in the compressed state adapting to the changing distance between electrodes during battery use, it is generally warped, and the relaxed state is different from the compressed state.

36. The battery separator according to claim 35, wherein, The battery separator further includes: a first plane formed by the tips of the first plurality of ribs; a second plane formed by the tips of the second plurality of ribs; a total thickness of at least 500 μm in the compressed state, which is the distance between the first plane and the second plane.

37. The battery separator according to claim 35, wherein, The battery separator further includes: a first plane formed by the tips of the first plurality of ribs; a second plane formed by the tips of the second plurality of ribs; a total thickness not exceeding 2.0 mm in the compressed state, which is the distance between the first plane and the second plane.

38. The battery separator according to claim 35, wherein, The battery separator further includes: a first plane formed by the tips of the first plurality of ribs; a second plane formed by the tips of the second plurality of ribs; a total thickness not exceeding 3.0 mm in the relaxed state, which is the distance between the first plane and the second plane.

39. The battery separator according to claim 35, wherein, The battery separator further includes: the total thickness in the relaxed state, which is equal to the sum of the first rib height of the first plurality of ribs, the second rib height of the second plurality of ribs, and the back net thickness; wherein, the first rib height is the distance from the back net to the tip of the first plurality of ribs, and the second rib height is the distance from the back net to the tip of the second plurality of ribs; the total thickness does not exceed 3.0 mm.

40. A lead-acid battery, comprising: A positive electrode, a negative electrode, and the battery separator as claimed in claim 1 disposed therebetween.

41. The lead-acid battery according to claim 40, wherein, The battery is one selected from the following: enhanced flooded lead-acid battery (EFB), flat plate battery, tubular battery, deep cycle battery, valve-regulated lead-acid (VRLA) battery, gel battery, absorbent glass mat (AGM) battery, inverter battery, stationary battery, energy storage battery for power generation, uninterruptible power supply (UPS) battery, battery with high cold cranking current (CCA) requirement, starting-lighting-ignition (SLI) vehicle battery, idle start-stop (ISS) vehicle battery, marine battery, truck battery, motorcycle battery, all-terrain vehicle battery, forklift battery, golf cart battery, hybrid electric vehicle (HEV) battery, light electric vehicle battery, neighborhood electric vehicle (NEV) battery, electric rickshaw battery, electric tricycle battery, electric bicycle battery, electric scooter battery.

42. A system with a battery, which includes the lead-acid battery as claimed in claim 40.

43. The system as claimed in claim 42, including one selected from: uninterruptible power supply (UPS), boat, truck, motorcycle, all-terrain vehicle, forklift, golf cart, hybrid electric vehicle (HEV), neighborhood electric vehicle (NEV), electric rickshaw, electric tricycle, electric bicycle, electric scooter.

44. A lead-acid battery, comprising: A positive electrode, a negative electrode, and a battery separator as claimed in any one of claims 1 to 39, the separator being a sheet, leaf, bag or fold, which is disposed between the two electrodes, or on at least one of them, or around at least one of them. Encapsulating at least one electrode with a non-woven, prematurely ruptured film, glass mat, sticker, strip, plate-like wrapper and / or case.

45. A lead-acid battery, comprising: A positive electrode, a negative electrode, and a battery separator as claimed in any one of claims 1 to 39, the separator being a sheet, leaf, bag or fold, which is disposed between the two electrodes, or on at least one of them, or around at least one of them. Not encapsulating at least one electrode with a non-woven, prematurely ruptured film, glass mat, sticker, strip, plate-like wrapper and / or case.

46. A vehicle, comprising the lead-acid battery as claimed in claim 44.

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