Improved lead acid battery separators, warp resistant separators, batteries, systems, and related methods

Abstract

What is needed are improved electrode plate and separator assemblies for lead-acid batteries, improved lead-acid cells or batteries incorporating the improved assemblies, systems or vehicles incorporating the improved assemblies and / or batteries, and related methods. [Solution] The electrode plates may have a grid formed by a stamping, casting, or expanded metal manufacturing process. The grid may have a non-uniform application of active material. The separator preferably provides a support structure to withstand or mitigate any plate warping or plate deflection.

Description

[Technical field]

[0001] Related Applications This application claims priority to and the benefit of U.S. Provisional Patent Application No. 62 / 719,185, filed August 17, 2018.

[0002] The present disclosure is directed to new or improved separators for various lead-acid batteries and / or systems. Exemplary embodiments disclosed herein are also directed to new or improved battery separators, warp resistant separators, battery cells incorporating such separators, batteries incorporating such separators, systems incorporating such separators, and / or methods of making and / or using such separators, new or improved lead-acid batteries, and / or combinations thereof. At least selected embodiments are directed to new or improved separators, batteries, and / or systems that provide improved battery life and / or reduced battery failure in lead-acid batteries, such as those having or operating with stamped plate electrodes, stamped grid electrodes, warped plate electrodes, or plate electrodes prone to warping, utilizing such new or improved separators. [Background technology]

[0003] As lead-acid batteries find their way into more and more applications and systems, size and weight become major considerations in their design. The goal is to reduce battery size and / or weight while at least maintaining or even increasing the capacity of larger prior art articles. Positive plates are typically constructed from lead dioxide (PbO2) (or alloys) grids doped with a positive active material ("PAM"). Negative plates are typically constructed from lead (Pb) (or alloys) grids doped with a negative active material ("NAM"). Lead (Pb) is the heaviest and most expensive element in lead-acid batteries, and battery designers continue to try to reduce the amount of lead in batteries to achieve the above goals. Historically, electrode grids were cast to produce rather thick electrodes. The industry later moved to expanded metal processes, which produced thinner electrodes than those produced by cast grid processes. Now, some modern batteries are constructed with stamped grids, producing even thinner electrodes than any previously known process.

[0004] While all of the above grid forming processes result in at least some amount of plate warping, none of the processes result in warped plates at the rate and severity seen in plates constructed with stamped grids. Warped plates create pinch points that can puncture the separator and cause shorting of the battery. Previous methods of mitigating the effects of warped plates have focused on the design of the grid itself. However, at least certain of these methods have yet to completely solve the problems associated with plate warping. As of yet, the inventors are unaware of a means of utilizing battery separators to solve the above problems. Summary of the Invention [Problem to be solved by the invention]

[0005] There remains a need for improved separators that provide reduced battery failure, improved battery cycle life, and / or improved performance, such as in partial states of charge, at least in certain applications or batteries, such as the exemplary conditions described above. More specifically, there remains a need for improved separators, improved batteries, and improved systems, such as those having separators with increased durability, separators with reduced incidence of punctures, batteries with reduced short circuit events, batteries with reduced water loss in the battery, batteries with lower battery float currents, batteries with improved battery operation in partial states of charge, batteries with improved battery life, batteries with reduced battery failure, improved batteries utilizing improved separators, systems utilizing improved batteries utilizing improved separators, and the like. More specifically, there remains a need for improved separators, improved batteries, and improved systems, e.g., those having or operating with stamping plates, stamping grids, non-uniform active materials, warped plates, or plates prone to warping, that provide improved battery life and / or reduced battery failure in lead-acid batteries, utilizing improved separators. [Means for solving the problem]

[0006] Details of one or more exemplary embodiments, aspects, or objects are set forth in the detailed description and claims set forth below. Other features, objects, and advantages will be apparent from the detailed description and claims set forth below. According to one or more selected embodiments, aspects, or objects, the present disclosure or invention at least addresses, and in some cases goes beyond, the problems, challenges, or needs set forth above.

[0007] According to at least select exemplary embodiments, aspects, or objectives, the present disclosure or invention may address at least the problems, issues, or needs set forth above, and / or may provide new or improved separators, warp resistant separators, and / or lead acid battery separators, new or improved cells or batteries utilizing the new or improved separators, and / or new or improved systems utilizing the new or improved separators, cells or batteries. According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to new or improved battery separators, battery cells, batteries, systems, and / or methods of making and / or using such new or improved battery separators, battery cells, batteries, and / or systems.

[0008] According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery having at least an improved construction and rib configuration for reducing or mitigating electrode plate warping and / or the effects of electrode plate warping; reduced occurrence of separator puncture; reduced occurrence of battery electrode shorting; etc.; and / or combinations thereof. According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery that may be characterized by at least one or more of: plate-warp resistance; puncture resistance; oxidation resistance; acid mixing; reduced electrical resistance; improved wettability; improved filler; optimized porosity; optimized tortuosity; reduced thickness; reduced backweb thickness; ribbed; anode side cross ribs; reduced oil content; increased acid diffusion; increased oxidation resistance or improved oxidation stability; optimized porosity; optimized pore tortuosity; improved acid diffusion; etc.; and / or combinations thereof. In accordance with at least certain example embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for lead-acid batteries that may provide at least one or more of: low water loss in batteries and / or battery cells; reduced electrical resistance in batteries and / or battery cells; increased acid mixing in batteries and / or battery cells; reduced acid stratification in batteries and / or battery cells; improved performance in batteries and / or battery cells; increased life in batteries and / or battery cells; reduced failure rates in batteries and / or battery cells; and / or combinations thereof.

[0009] According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to separators and / or improved battery cells and / or batteries utilizing the improved separators, and / or improved systems utilizing the improved battery cells and / or batteries utilizing the improved separators, that overcome at least the problems and / or challenges noted above. For example, and by way of example only, the improved battery cells and / or batteries may be characterized by at least one or more of: improved performance; reduced failure rates; improved life span; reduced plate shorting occurrences; reduced separator puncture occurrences; reduced water loss; reduced float current; improved charge termination current; increased charge acceptance; improved energy throughput; reduced antimony (Sb) poisoning; reduced acid stratification; reduced acid starvation; reduced dendrite formation; reduced internal electrical resistance; improved cold cranking amps ("CCA"), improved uniformity; improved cycle performance; and / or combinations thereof.

[0010] According to at least select example embodiments, aspects, or objectives, the present disclosure or invention is directed to at least new or improved battery separators, warp resistant separators, puncture resistant separators, elastomeric separators, battery cells, batteries, methods involving same, systems using same, vehicles using same, methods of manufacturing same, methods of using same, and combinations thereof.

[0011] In accordance with at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to new or improved battery separators for use in a variety of batteries and / or applications, including an exemplary list of: flat plate batteries; tubular batteries; flooded lead acid batteries; reinforced flooded lead acid batteries ("EFB"); valve regulated lead acid ("VRLA") batteries; deep cycle batteries; gel batteries; absorbent glass mat ("AGM") batteries; inverter batteries; current collector batteries; storage batteries; internal combustion engine batteries; auxiliary batteries; starting-lighting-ignition ("SLI") batteries; idle-start-stop ("ISS") batteries; vehicle batteries; passenger car batteries; automobile batteries; truck batteries; batteries; motorcycle batteries; all-terrain vehicle batteries; marine batteries; aircraft batteries, forklift batteries; golf cart or golf car batteries; hybrid electric vehicle ("HEV") batteries; micro-hybrid vehicle batteries; electric vehicle batteries; electric rickshaw batteries; electric tricycle batteries; electric bicycle batteries; uninterruptible power supply ("UPS") batteries; batteries with high CCA requirements; batteries operating in partial state of charge ("PSoC"); etc; and combinations thereof.

[0012] According to at least selected exemplary embodiments, aspects, or objectives, numerous systems are provided that include the inventive battery incorporating the inventive separator described herein. Exemplary systems may be one or more of: vehicles; UPS; auxiliary power systems; current collector systems; renewable energy current collector systems; wind energy current collector systems; solar energy current collector systems; backup power systems; inverters; and combinations thereof. Further, exemplary vehicles may be one of: automobiles; cars; trucks; forklifts; hybrid vehicles; HEVs; micro-hybrid vehicles; ISS vehicles; electric vehicles; water containers; aircraft; electric rickshaws; electric tricycles; electric bicycles; motorcycles; all-terrain vehicles; golf carts or golf cars; and the like; and combinations thereof.

[0013] In a first exemplary embodiment of the present disclosure or invention, the electrode and separator assembly includes an electrode plate having a grid and an active material thereon. The grid includes at least one grid edge. Furthermore, the active material may be non-uniformly distributed on the grid. In another embodiment, the grid may be thinner than approximately 1.00 mm. In yet another embodiment, the grid may have a non-uniform geometry.

[0014] A porous membrane is disposed adjacent to the electrode plate having a first membrane surface having a first surface edge and a second surface edge and a plurality of ribs extending from the membrane surface;

[0015] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly may be either a positive or negative electrode and includes an electrode plate having a grid and an active material non-uniformly distributed thereon. The grid includes a first grid edge and a second grid edge. The porous membrane is disposed adjacent to the electrode plate. The porous membrane has a first side lane adjacent to the first membrane edge and a second side lane adjacent to the second membrane edge, and a central portion disposed between the first and second side lanes. The porous membrane includes a first membrane surface having a plurality of primary ribs extending from or into the first membrane surface in the central portion, and a first array of secondary ribs disposed in the first side lane and a second array of secondary ribs disposed in the second side lane.

[0016] In one embodiment of the invention, the first grid edge may be disposed in the first side lane and the second grid edge may be disposed in the second side lane. The plurality of primary ribs may have a uniform height and uniform distribution. Meanwhile, either or both of the first array of secondary ribs and the second array of secondary ribs are more densely packed than the plurality of primary ribs. The plurality of primary ribs, the first array of secondary ribs, and / or the second array of secondary ribs may be longitudinally disposed substantially parallel to the length of the porous membrane, or laterally disposed substantially parallel to the width of the porous membrane. Either or both of the first array of secondary ribs and the second array of secondary ribs may be substantially parallel, orthogonal, or angled to the plurality of primary ribs. The porous membrane may have a second membrane surface having a third array of ribs thereon.

[0017] In another aspect of the invention, the grid may be a stamped grid, a cast grid, or an expanded metal grid. Additionally, the grid may be prone to warping. The grid may have a first grid surface and a second grid surface, and the active material may be more highly distributed on the first grid surface compared to the second grid surface. Additionally, the active material may be non-uniformly distributed on the surface of the grid.

[0018] In yet another embodiment, any of the plurality of primary ribs, the first array of secondary ribs, the second array of secondary ribs, and / or the third array of ribs may be one or more of: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs that may extend longitudinally in a substantially longitudinal direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof.

[0019] In certain embodiments, the porous membrane may be one of an envelope, a hybrid envelope, a sleeve separator, a pocket separator, and a wrap separator. The porous membrane may have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesive, and combinations thereof. The porous membrane may be a cut piece.

[0020] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly comprises an electrode plate, which may be either a positive or negative electrode, and has a grid and active material non-uniformly distributed thereon. The porous membrane may comprise a first membrane surface having an array of primary ribs disposed on such first membrane surface and extending from a first membrane edge to a second membrane edge; the array of primary ribs has a uniform height.

[0021] Another aspect of the present invention or disclosure provides a grid having a first grid surface and a second grid surface, and the active material is more highly distributed on the first grid surface compared to the second grid surface. Alternatively, or in addition, the active material may be non-uniformly distributed on the surface of the grid. The grid may be one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid. Also, the grid may be prone to warping. Either the first film surface or the second film surface may be adjacent to an electrode plate.

[0022] In another aspect of the invention or disclosure, the array of primary ribs may be disposed longitudinally and substantially parallel to the length of the porous membrane and may be uniformly or non-uniformly spaced laterally across the width of the porous membrane. The porous membrane may have a second surface from which a second array of ribs extends.

[0023] In another embodiment of the present invention or disclosure, either or both of the primary array of ribs and / or the second array of ribs may be one or more of: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs that may extend longitudinally in a substantially longitudinal direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the porous membrane, ribs that may extend transversely in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof.

[0024] In one exemplary embodiment, the porous membrane may be one of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator; the envelope, hybrid envelope, sleeve separator, pocket separator, and wrap separator may have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

[0025] In yet another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly may include an electrode plate having a grid and an active material. The grid may have a first grid edge and a second grid edge, and the active material may be non-uniformly distributed on the grid. The porous membrane may further include a first membrane surface having a support structure supporting the first grid edge and the second grid edge. The first grid edge may have at least a first grid corner, and the second grid edge may have at least a second grid corner. The support structure may have a first array of ribs having a uniform height.

[0026] The grid may have a first grid surface and a second grid surface, and the active material may be more highly distributed on the first grid surface compared to the second grid surface. Alternatively, or in addition, the active material may be non-uniformly distributed on the surface of the grid. The grid may be one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid. The electrode plate may be prone to warping.

[0027] In certain exemplary embodiments, the first array of ribs may be uniformly spaced laterally from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane. The first array of ribs may also be uniformly or non-uniformly spaced laterally from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane.

[0028] In other exemplary embodiments of the present disclosure, the first array of ribs may be more densely packed in a first membrane region adjacent a first membrane edge and more densely packed in a second membrane region adjacent a second membrane edge compared to the ribs spaced apart in a central portion of the porous membrane.

[0029] In yet another exemplary aspect of the present disclosure, the first array of ribs may be uniformly or non-uniformly spaced laterally from a first grid edge to a second grid edge, and the first array of ribs may be more densely packed in a first region adjacent the first grid edge and more densely packed in a second region adjacent the second grid edge compared to the ribs spaced apart in a central portion of the grid.

[0030] In yet another aspect of the present disclosure, the support structure may have a fiber mat; the fiber mat may extend from a first grid edge to a second grid edge. The support structure may have a first fiber mat adjacent to the first grid edge and a second fiber mat adjacent to the second grid edge.

[0031] In another exemplary embodiment, the porous membrane can be one of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator; the envelope, hybrid envelope, sleeve separator, pocket separator, and wrap separator can have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

[0032] In yet another exemplary embodiment of the present disclosure, a lead-acid battery may comprise a separator substantially as described herein. The lead-acid battery may be operated in one of the following states: driving, stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial state of charge, and combinations thereof.

[0033] Exemplary batteries may be one of: a flat plate battery, a flooded lead acid battery, an reinforced flooded lead acid battery ("EFB"), a valve regulated lead acid ("VRLA") battery, a deep cycle battery, a gel battery, an absorbent glass mat ("AGM") battery, a tubular battery, an inverter battery, a vehicle battery, a starting-lighting-ignition ("SLI") vehicle battery, an idle-start-stop ("ISS") vehicle battery, an automobile battery, a truck battery, a marine battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric car battery, an electric rickshaw battery, an electric three-wheeler battery, and an electric bicycle battery;

[0034] In yet another exemplary embodiment, the system may comprise a lead-acid battery as described herein. The system may comprise a vehicle, which may be one of an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart, a hybrid vehicle, a hybrid electric vehicle, an electric vehicle, an idle-start-stop ("ISS") vehicle, a water container, an electric rickshaw, an electric three-wheeler, and an electric bicycle. Additionally, the system may operate in one of the following states: while driving, while stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial charge state, and combinations thereof. The system may further be one of the following: an uninterruptible power supply, an energy storage system, a power backup system, a renewable energy storage system, and combinations thereof.

[0035] In yet another exemplary embodiment, a method for mitigating grid warpage in an electrode and separator assembly may be provided. The method may provide an electrode plate having a grid susceptible to warping; and position a support structure adjacent to the grid. The support structure may include a battery separator. Additionally, the support structure may include a fiber mat or mesh. The active material may be non-uniformly applied to the grid. The grid may have a perimeter. The support structure may overlap at least a portion of the grid perimeter. The support structure may be provided as a set of ribs extending from a porous membrane having a uniform height. The set of ribs may be longitudinally disposed in a machine direction of the porous membrane, and the set of ribs may be equally spaced in a lateral dimension in a width direction from a first edge of the perimeter to a second edge of the perimeter. Alternatively or in addition, the support structure may include or be a polygonal spacer. Alternatively or in addition, the support structure may include or be a fiber mat. Alternatively, or in addition, the support structure may include or be a first fiber mat and a second fiber mat, the first fiber mat disposed to at least partially overlap a first edge of the periphery; and the second fiber mat disposed to at least partially overlap a second edge of the periphery. The method may further provide for subjecting the electrode and separator assembly to elevated temperatures and / or thermal cycling.

[0036] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention provides a separator whose components and physical attributes and features combine synergistically to address in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a battery using the separator described herein that addresses in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved lead-acid battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a system using the battery described herein that addresses in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved system utilizing the inventive lead-acid battery utilizing the inventive separator described herein.

[0037] In accordance with at least selected exemplary embodiments, aspects, or objectives, the present invention solves, meets, and / or overcomes at least a problem, need, and / or challenge heretofore unsolved, unmet, and / or unaddressed in the state of the art. In accordance with at least certain objectives, the present invention provides an improved separator, an improved battery utilizing the improved separator, and / or an improved system using the improved battery that overcomes at least the problems set forth above. [Brief description of the drawings]

[0038] [Figure 1A] FIG. 1A is a schematic diagram of a typical lead-acid battery. [Figure 1B] FIG. 1B shows a rib pattern disposed longitudinally on the separator in the machine direction md. [Figure 1C] FIG. 1C shows a rib pattern disposed laterally on the separator in the cross-machine direction cmd. [Figure 2A] FIG. 2A shows an exemplary electrode and separator assembly. [Figure 2B] FIG. 2B shows an exemplary electrode and separator assembly. [Diagram 3] FIG. 3 shows an exemplary lead-acid battery plate. [Figure 4A] FIG. 4A shows a lead-acid battery plate with various types of active materials applied. [Figure 4B] FIG. 4B shows a lead-acid battery plate with various types of active materials applied. [Figure 4C] FIG. 4C shows a lead-acid battery plate with various types of active materials applied. [Figure 4D] FIG. 4D shows a lead acid battery plate with various types of active materials applied. [Figure 4E] FIG. 4E shows a lead acid battery plate with various types of active materials applied. [Figure 4F] FIG. 4F shows a lead-acid battery plate with various types of active materials applied. [Figure 4G] FIG. 4G shows a lead acid battery plate with various types of active materials applied. [Figure 5A] FIG. 5A is a plan view of a cambered plate. [Figure 5B] FIG. 5B is a side view of the cambered plate of FIG. 5A. [Figure 5C] FIG. 5C shows adjacent electrode plates and separator assemblies with cambered plates and the pinch points they create. [Figure 6A] FIG. 6A shows various exemplary separator and rib profiles that resist plate warping. [Figure 6B] FIG. 6B shows various exemplary separator and rib profiles that resist plate warping. [Figure 7A] Figure 7A shows various exemplary electrode plate and separator assemblies having an exemplary inventive separator of the present invention, generally as shown in Figures 1B and 1C. [Figure 7B]Figure 7B shows various exemplary electrode plate and separator assemblies having an exemplary inventive separator of the present invention, generally as shown in Figure 6A. [Figure 7C] Figure 7C shows various exemplary electrode plate and separator assemblies having an exemplary inventive separator of the present invention, generally as shown in Figure 6B. [Figure 8A] FIG. 8A shows a conventional separator sagging due to active material swelling. [Figure 8B] FIG. 8B shows a conventional separator sagging due to active material swelling. [Figure 8C] FIG. 8C shows a separator of the present invention that resists active material swelling. [Figure 8D] FIG. 8D shows a separator of the present invention that resists active material swelling. [Figure 9A] FIG. 9A illustrates an exemplary inventive rib profile for an exemplary inventive separator. [Figure 9B] FIG. 9B illustrates an exemplary inventive rib profile for an exemplary inventive separator. [Figure 10A] FIG. 10A shows the electrode surface and the portion supported by the separator of the present invention. [Figure 10B] FIG. 10B shows the electrode surface and the portion supported by the separator of the present invention. [Figure 11] FIG. 11 is a graph and chart showing the attrition properties of the silica of the present invention. [Figure 12A] FIG. 12A shows a sample and test jig for testing the oxidation resistance of a material. [Figure 12B] FIG. 12B shows a sample and a test jig for testing the oxidation resistance of a material. [Figure 12C] FIG. 12C shows a sample and a test jig for testing the oxidation resistance of the material. [Figure 13]FIG. 13 shows the puncture tip. The same or corresponding elements or parts are designated by like reference characters throughout the figures. Unless otherwise stated, none of the figures should be construed as being to scale. Dimensions represented in the various figures are in millimeters. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] Detailed Description According to at least selected exemplary embodiments, objectives, or aspects, the present disclosure or invention addresses and in some cases exceeds the above problems or needs. According to at least certain exemplary embodiments, objectives, or aspects, the present disclosure or invention may provide an improved separator, and a battery cell and / or battery using the same; and / or an associated system using the same; and / or an associated method using the same. According to at least selected exemplary embodiments, aspects, or aspects, the present disclosure or invention is directed at at least a new or improved battery separator characterized by one or more of: a plate-warp resistant separator; a puncture resistant separator; an elastic separator; a battery cell; a battery; an associated method using or involving the same; an associated system using or involving the same; an associated vehicle using or involving the same; a method of manufacturing the same; and / or a combination thereof. In accordance with at least select example embodiments, aspects, or objectives, the present disclosure or invention is directed to one or more new or improved battery cells and / or batteries characterized by one or more of: improved performance; reduced failure rates; improved life span; reduced occurrence of plate shorting; reduced occurrence of separator punctures; and / or the like; and / or combinations thereof.

[0040] 1A, an exemplary lead-acid battery 100 includes an array 102 of alternating positive plates 200 (or multiple positive plates) and negative plates 201 (or multiple negative plates) with a separator 300 between each electrode 200, 201. The array 102 is substantially immersed in an electrolyte 104. The electrolyte 104 may be, for example, a solution of sulfuric acid (H2SO4) and water (H2O). The electrolyte may have, for example, a specific gravity of approximately 1.28 with a specific gravity ranging from approximately 1.215 to approximately 1.300. The battery 100 further includes a positive terminal 104 in electrical communication with the positive plate 200 and a negative terminal 106 in electrical communication with the negative plate 201.

[0041] 1B and 1C, an exemplary separator 300 may include a porous membrane backweb 302 having an array of ribs 304, 305 extending therefrom. As shown in FIG. 1B, an exemplary first array of ribs 304 is disposed longitudinally in the machine direction md of the separator 300. As shown in FIG. 1C, an exemplary second array of ribs 305 is disposed laterally in the width direction cmd of the separator 300 and may therefore be referred to as cross ribs. When placed in a battery, the exemplary separator 300 may have a first array of ribs 304 adjacent the positive plate 200 and may be referred to as positive ribs 304, while a second array of ribs 305 adjacent the negative plate 201 and may be referred to as negative ribs, or vice versa. 1C, the second array of ribs may be referred to as cross ribs when they extend in the width direction cmd (e.g., "negative cross ribs" when facing the negative plate 201). Additionally, either array of ribs 304, 305 may face either plate 200, 201 when disposed within the battery 100.

[0042] Any of the arrays of ribs 304, 305 may be solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, inclined ribs, linear ribs, ribs extending longitudinally in substantially the machine direction md of the separator (i.e., running from the top to the bottom of the separator 300 in the cell), ribs extending laterally in substantially the width direction cmd of the separator (i.e., perpendicular to the machine direction md, running from the side of the separator 300 in the cell), ribs extending laterally in substantially the width direction cmd of the separator 300, discrete teeth, The ribs 304, 305 may be configured in numerous configurations, shapes, profiles, or patterns that may be uniform sets, alternating sets, or mixtures or combinations of ribs, toothed ribs, sawtooth ribs, crested ribs, crested ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, interrupted discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini ribs, cross mini ribs, and combinations thereof. The ribs 304, 305 are further described herein.

[0043] Figures 2A and 2B show two exemplary electrode / separator assemblies 400 as vertical cross-sectional views taken along an axis substantially parallel to the width of the separator. Figure 2A shows an exemplary electrode / separator assembly 400 having a typical wrap or envelope separator. Figure 2B shows an exemplary electrode / separator assembly having a typical leaf or cut piece separator. Exemplary embodiments of separator placement within a battery are described further herein.

[0044] Board Composition 2A-4G, the electrode plate 200, 201 is made of at least a grid 202 and an active material 203. The grid 202 may be made in various ways, for example, cast metal, expanded metal, and stamped metal. Also, the various grids in the battery may be made differently from each other. For example, the positive grid may be stamped, while the negative grid is expanded metal. As described above, stamped grids are less lead-based than other methods and therefore more cost-effective. Although stamped grids reduce cost, thinner plates may warp, deform, bend, twist, bend, and / or distort. Furthermore, grids with non-uniform geometries and non-uniformly distributed active materials are also more prone to warp, deform, bend, twist, bend, and / or distort. This leads to potential pinch points, wear points, or puncture points. When the plate(s) cut or puncture through the separator, they may come into contact with adjacent plates, shorting out the battery and / or battery cells, and are highly susceptible to shorting. Without wishing to be limited by theory, the inventors believe that grids thinner than approximately 1.00 mm are most susceptible to warping, with grids thinner than approximately 0.85 mm being preferred, and grids thinner than approximately 0.70 mm being most susceptible to warping.

[0045] As used herein, throughout the detailed description and in the claims, the term "warp" and variations thereof, in addition to having its ordinary and accustomed meaning, may be used interchangeably with at least the following terms and variations thereof: deform; bend; twist; bend; and / or distort, which also have their ordinary and accustomed meanings.

[0046] 2A-4G, grid 202 is typically doped or pasted with an active material 203. Positive plate 200 is typically doped with a positive active material ("PAM") and negative plate 201 is typically doped with a negative active material ("NAM"). The active material 203 increases the functionality of the grid.

[0047] 3, an exemplary grid 202 includes a main grid portion 202a and a connector 202b for a lead strap within the battery. The exemplary exemplary main grid portion 202a has a first vertical side edge 204a, a second vertical side edge 204b, a bottom horizontal edge 204c, and a top horizontal edge 204d. The exemplary main grid portion 202a further includes four corners 206a, 206b, 206c, 206d, which may or may not be rounded. The main grid portion 202a further includes latticework that creates a series of openings through the grid 208. This helps reduce weight and materials and better utilizes the entire grid during the electrochemical reaction of the battery.

[0048] 4A-4G, plates 200, 201 are shown with grids 202 having active material 203 that is imperfectly disposed with varying degrees of uniformity. FIGS. 4A-4C are side views of plates 200, 201. FIG. 4A shows a substantially uniform distribution of active material 203 in grid 202. FIG. 4B shows a slightly uneven distribution with more active material 203 on the right side of grid 202 as opposed to the left. FIG. 4C shows a more severely uneven distribution with more active material 203 on the right side of grid 202 as opposed to the left. FIGS. 4D-4G show exemplary plates 200, 201 with imperfect distribution of active material across the face of the grid. Darker areas may represent application of more active material than lighter areas. FIG. 4D shows a symmetrical distribution of active material. FIG. 4E shows an asymmetrical distribution of active material. FIG 4F shows bimodal, symmetrically distributed active materials. FIG 4G shows exemplary manners in which the plates 200, 201 may warp as indicated by the arrows. It is recognized that the warped plates 200, 201 may warp, curve or bend along or about any axis relative to the grid 202. It is further recognized that the warped plates 200, 201 may warp, curve or bend along or about multiple axes relative to the grid 202.

[0049] For example, Figures 5A and 5B show exemplary cambered electrode plates 200, 201. This particular plate 200, 201 is shown cambered about a single axis 210, although camber in multiple axes may occur. Figure 5C is a top-down cross-sectional view of an array 102 of separator / electrode assemblies 400. The array is shown with two positive plates 200, two negative plates 201, and a typical commercially known separator 300 that is not designed to accommodate a cambered plate that envelopes the positive plate 200. Because the plates 200, 201 are assumed to be cambered and not flat, they may cut or wear through the separator 300 for the plates 200, 201 and contact each other, creating pinch points 402 that may short out the cell and / or battery in which they are located.

[0050] The inventors have further realized that high grid erosion at partial charge states and cycling conditions also tend to exacerbate plate warping. Therefore, exemplary separators are defined herein that help mitigate grid erosion. It is believed that imperfect distribution of active material in the grid creates a situation of uneven expansion and contraction of the plate during cycling, which causes the plate to warp.

[0051] Separator Description Exemplary separators may comprise webs of porous membranes, e.g., 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 membranes may preferably have pore sizes from submicron up to 100 μm, and in certain embodiments between about 0.1 μm and about 10 μm. The porosity of the separator membranes described herein may be greater than 50% to 60% in certain embodiments. In certain select embodiments, the porous membrane may be flat or have ribs extending from its surface.

[0052] The exemplary separator 300 may be provided as a flat sheet, leaf(s), wrap, sleeve, or envelope or pocket separator. The exemplary envelope separator may preferably have a bottom edge 301c that is folded, crinkled, sealed, etc., and the side edges 301a, 301b may be continuously or intermittently sealed edges. The edges may be bonded or sealed by adhesive, heat, ultrasonic welding, etc., or combinations thereof. The exemplary envelope separator may envelop the positive electrode (i.e., a positive electrode envelope separator), such that the separator has two insides facing the positive electrode and two outsides facing the adjacent negative electrode. Alternatively, another exemplary envelope separator may envelop the negative electrode (i.e., a negative electrode envelope separator), such that the separator has two insides facing the negative electrode and two outsides facing the adjacent positive electrode. In certain exemplary embodiments, the battery may utilize one or both of a positive electrode envelope separator, a negative electrode envelope separator.

[0053] Certain exemplary separators may be processed to form a hybrid envelope. The hybrid envelope may include one or more slits or openings formed before, during or after folding the separator sheet in half and / or before, during or after gluing or sealing the edges of the separator sheet to form the envelope. The slits or openings may be located within any closed edge of the separator, e.g., within the sealed edge, but preferably within the bottom fold. The top of the separator typically remains open. The length of the openings may be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the length of the entire closed edge. The length of the openings may be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5 or 1 / 10 to 1 / 5 of the total length of the closed edge. The hybrid envelope may have 1 to 5, 1 to 4, 2 to 4, 2 to 3 or 2 openings, which may or may not be equally spaced along the length of the sealed edge. It is preferred that there are no openings at the corners of the envelope.

[0054] rib As described above, an exemplary separator 300 may have a first array 304 of ribs adjacent to the positive plate 200, while a second array 305 of ribs adjacent to the negative plate 201, or vice versa. Additionally, either array 304, 305 may take a number of forms.

[0055] For example, the arrays of either or both of ribs 304, 305 may be solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, inclined ribs, linear ribs, ribs that extend longitudinally in substantially the machine direction md of the separator (i.e., running from the top to the bottom of the separator 300 in the battery 100 (see FIG. 1A )), ribs that extend laterally in substantially the width direction cmd of the separator (i.e., perpendicular to the machine direction md, running laterally in ... the separator 300 in the battery 100 (see FIG. 1A )), ribs that extend laterally in the separator 300 in the battery 100 (see FIG. 1A )), ribs that extend laterally in the separator 300 in the battery 100 (see FIG. 1A ). The actuator may be a uniform set, alternating set, or mixture or combination of ribs extending substantially transversely in the width direction, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, interrupted discontinuous zigzag-sawtooth ribs, grooves, channels, textured areas, embossments, embossed ribs, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini ribs, cross mini ribs, and any combination thereof.

[0056] Additionally, the ribs 304, 305 may be a plurality of ribs, preferably broken ribs, defined by an angle that is neither parallel nor perpendicular to the edge of the separator. In other words, the angle may be defined as between zero degrees (0°) and less than one hundred and eighty degrees (180°) or between one hundred and eighty degrees (180°) and less than three hundred and sixty degrees (360°) relative to the lengthwise direction of the separator. Also, the angle may be defined as between zero degrees (0°) and less than one hundred and eighty degrees (180°) or between one hundred and eighty degrees (180°) and less than three hundred and sixty degrees (360°) relative to the widthwise direction of the separator. The angled rib pattern may be an optionally preferred Daramic® RipTide™ acid blend rib profile that may help reduce, mitigate, or eliminate acid stratification in certain batteries. The selection of a mixture of rib profiles tends to perform best when the exemplary battery is in operation, preferably during stop and start operation, and the porous membrane 302 is substantially aligned and parallel to the vector of motion.

[0057] In certain exemplary embodiments, the ribs 304 in Figure 1B may face the positive plate when placed in an exemplary battery, and therefore may be referred to as positive ribs 304. The ribs 305 in Figure 1C may face the negative plate when placed in an exemplary battery, and therefore may be referred to as negative ribs 305.

[0058] In select exemplary embodiments, at least a portion of the negative ribs may preferably have a height of about 5% to about 100%, or even more than 100%, of the height of the positive ribs. In some exemplary embodiments, the negative rib height may be at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95%, or 100% of the positive rib height. In other exemplary embodiments, the negative rib height may be approximately 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% or less compared to the positive rib height.

[0059] In some select embodiments, at least a portion of the porous membrane may have anode ribs that are longitudinal, transverse, or cross ribs. The anode ribs may be parallel to the separator width direction cmd or may be disposed at an angle to that direction. For example, the anode ribs may be oriented at approximately 0°, 5°, 15°, 25°, 30°, 45°, 60°, 70°, 80°, or 90° to the width direction cmd. The cross ribs may be oriented at approximately 0° to approximately 30°, approximately 30° to approximately 45°, approximately 45° to approximately 60°, approximately 30° to approximately 60°, approximately 30° to approximately 90°, or approximately 60° to approximately 90° to the width direction cmd.

[0060] 1B and 1C, either array 304, 305 may extend uniformly along the width of the separator 300 from the first lateral edge 301a to the second lateral edge 301b. This is known as a universal profile.

[0061] Alternatively, referring to Figures 6A and 6B, an exemplary separator of the present disclosure may have a central portion 306a with ribs 304b disposed therein or no ribs at all, and side lanes 306b adjacent the lateral longitudinal edges 301a, 301b, where the side lanes 306b are flat. The ribs 304a in the central portion 306a may be referred to as primary ribs, and the ribs 304b in the side lanes 306b may be referred to as secondary ribs. These secondary ribs 304b may be more closely spaced than the primary ribs 304a, may be smaller than the primary ribs 304a, may be larger than the primary ribs 304a, or a combination thereof. For example, the secondary ribs 304b may be about 25% to about 100% or more than about 100% of the height of the primary ribs 304a, may be more closely spaced compared to the spacing of the primary ribs 304a, or a combination thereof. As further shown in Figures 6A and 6B, the example secondary ribs 304b may be longitudinally disposed and aligned with the machine direction md (Figure 6A) or laterally disposed and aligned with the width direction cmd (Figure 6B). Although not shown, the example secondary ribs 304b may be disposed at an angle relative to the machine direction cmd and width direction cmd. The example secondary ribs 304b may be uniformly disposed at a common angle or the angle may vary among the secondary ribs 304b, for example, to potentially create a pattern.

[0062] As further shown in Figures 6A and 6B, the outline of the electrode plates 200, 201 is shown in dashed lines overlaid with their location in the separator 300. As shown, the plate corners 206a, 206b, 206c, 206d are preferably contained, or at least partially contained, within the side lanes 306b. Thus, the secondary ribs 304b help to hold the corners 206a, 206b, 206c, 206d parallel when the plate separator assembly 400 is compressed when placed in a battery. The vertical plate edges 204a, 204b are also preferably contained, or at least partially contained, within the side lanes 306b. Thus, the secondary ribs 304b help to hold the vertical plate edges 204a, 204b parallel when the plate separator assembly 400 is compressed when placed in a battery. It is further envisioned that the side lanes 306b may have a thicker substrate underneath the ribs as compared to the substrate in the central portion 306a.

[0063] The side lane 306b may further aid in sealing an edge of the exemplary separator 300 to another edge of the separator 300, as is done when enveloping the separator 300, as discussed herein. For example, the seal 308 (as shown by the superimposed dashed line) may run through at least a portion of the side lane 306b.

[0064] 7A-7C, an exemplary inventive electrode plate and separator assembly 400 is shown along with various separators 300. As shown, positive plate 200 is enveloped such that positive ribs 304, 304a, 304b are adjacent to plate 200. It is understood that plate 200 could also be a negative plate, although not in the configuration shown.

[0065] With reference to FIG. 7A, an exemplary plate and separator assembly 400 includes a separator 300 having a universal profile. The ribs 304 may coincide with the lateral edges of the plate 200. With reference to FIG. 7B, an exemplary plate and separator assembly 400 includes a separator having primary ribs 304a and secondary ribs 304b. The secondary ribs 304b are shown running substantially parallel to the longitudinal direction and substantially perpendicular to the width direction cmd. The lateral edges of the plate 200 are preferably contained or at least partially contained within the side lanes 306b. With reference to FIG. 7C, an exemplary plate and separator assembly 400 includes a separator having primary ribs 304a and secondary ribs 304b. The secondary ribs 304b are shown running substantially parallel to the width direction cmd and substantially perpendicular to the longitudinal direction. The lateral edges of the plate 200 are preferably contained or at least partially contained within the side lanes 306b.

[0066] As depicted in FIGS. 7A-7C, separator 300 may be formed into an envelope as generally described herein by sealing the separator edges at lines depicted as joints.

[0067] Specific goals of the present invention include minimizing the effects of negative electrode active material ("NAM") swelling, which tends to cause acid starvation, while taking advantage of any operation that may facilitate the battery to maximize acid mixing and reduce the effects of acid stratification, both of which are problems exhibited by batteries operated at a partial state of charge.

[0068] The inventors have found that one way to minimize the effects of NAM swelling is to maximize separator elasticity, for example, to reduce the likelihood that the NAM will cause the porous backweb to flex into the PAM. A specific way to increase separator elasticity is to increase the porous membrane backweb thickness. This, however, also increases the electrical resistance of the separator, which negatively impacts the performance of the battery (loss of the thicker backweb, for one thing). The inventors have found that increasing the contact points between the separator and the positive electrode acts to strengthen the backweb between the contact points. Increasing the number of ribs to achieve this goal also increases the amount of contact area between the separator and the positive electrode. Minimizing the contact area is said to lower the electrical resistance of the separator and also open up more electrode surface area to the electrolyte for the electrochemical reactions that provide the functionality of the battery. The reduced contact area is also said to reduce the opportunity for dendrites to form through the separator and cause electrical shorts. The issue of dendrite formation is discussed below. A further goal is to maximize electrolyte or acid mixing for the battery used in operation to minimize the effects of acid stratification. Furthermore, solid ribs do not facilitate the goal of acid mixing to reduce acid stratification.

[0069] The inventors have found that, as a select exemplary preferred embodiment, the separator may include elastic means to resist or mitigate backweb deflection under the forces and pressure exerted by NAM swelling, which leads to oxygen starvation, by maximizing the number of contact points while simultaneously minimizing the contact area between the separator and adjacent electrodes. The inventors have found that another select exemplary embodiment may provide a separator with acid mixing means to reduce, mitigate or reverse the effects of acid stratification by maximizing the number of distinct contact points between the separator and adjacent electrodes. Another select exemplary embodiment may provide a separator with dendrite mitigation means to reduce or mitigate lead sulfate (PbSO4) dendrite growth. The inventors have determined that such elastic means, acid mixing means, and dendrite mitigation means may be addressed, achieved, or at least partially addressed and / or achieved by the design of the rib structure. Accordingly, select embodiments described herein provide elastic means, acid mixing means, and dendrite mitigation means that balance these parameters to achieve desired goals, and / or rely on rib structures to at least partially address and / or achieve the balance of these parameters and / or the desired elastic means, acid mixing means, and / or dendrite mitigation means.

[0070] 8A and 8B, a typical commercially available separator 300 is shown disposed between the positive plate 200 and the negative plate 201, and although not shown, the assembly is assumed to be in a battery and submerged in electrolyte 104. For convenience, the negative side ribs are omitted. FIG. 8A shows the porous membrane 302 with the positive plate 200 facing side 302p and the negative plate 201 facing side 302n. As shown in FIG. 8B, cycling of the battery causes the active material in the plates 200, 201 to swell, deflecting the porous membrane 302 between the ribs 304. As shown, the negative active material of the negative plate 201 swells and deflects the separator towards the positive plate 200. At the same time, the positive active material of the positive plate 200 swells in conjunction with the negative plate swelling, forcing a substantial portion of the electrolyte 104 out of the space between the plates 200, 201. This condition is known as acid starvation, or electrolyte starvation, and seriously impedes the life and performance of a lead-acid battery.

[0071] 8C and 8D, an exemplary improved inventive separator 300 of the present invention is shown to mitigate the acid deficiency typically imparted by previously known battery separators. As shown in FIGS. 8A and 8B, the primary or positive rib 304 of a typical commercially available separator 300 is spaced apart from the first rib spacing (first spacing PosRib ) and the first rib tip width (first tip W Pos 8C and 8D, the positive electrode side ribs 304 are shown having a second rib spacing (second spacing PosRib ) and the second rib tip width (second tip W Pos8C ). Although not drawn to scale, the second spacing and second tip width are shorter and smaller in dimension than the first spacing and first tip width. This maximizes the number of distinct contact points between the inventive separator 300 and the adjacent electrodes 200, 201 while simultaneously minimizing the contact area between them. As can be seen in FIG. 8C , the swollen electrodes 200, 201 do not flex the separator and expel comparable electrolyte between the electrodes compared to that of the conventional separators shown in FIGS. 8A and 8B . Referring now to FIG. 8D , the inventive separator 300 is shown substantially similar to FIG. 8C but with anode side rib 305 that further spaces the porous membrane 302 away from the anode 201 . This prevents or at least reduces the porous membrane 302 from flexing in any way, further reducing the effects of oxygen starvation. As described herein, the ribs 304, 305 may be of various heights and widths and are not necessarily dependent on one another. Additionally, the positive ribs 304 may be spaced apart at different intervals than the negative ribs 305 .

[0072] 9A and 9B, one particular exemplary embodiment of the inventive separator 300 comprises an array of positive side ribs that may comprise a rib base (rib base) that extends the length of the separator in the machine direction md. Spaced apart teeth, discontinuous peaks, or other protrusions (teeth) may extend from the surface of the rib base, such that the teeth are elevated above the supporting structure surface of the porous membrane backweb (backweb). Additionally, the rib base may be wider than the teeth themselves. The positive side ribs are spaced apart with a typical spacing (spacing) of approximately 2.5 mm to approximately 6.0 mm. PosRib ) run substantially parallel to one another, with a typical spacing of approximately 3.5 mm. The height of the positive electrode side ribs (teeth and base height) measured from the surface of the porous membrane backweb PosRib9B ) from about 10 μm to about 2.0 mm, with a typical height of about 0.5 mm. Exemplary rib teeth on adjacent ribs may be substantially in-line with one another. However, as shown in FIG. 9B , exemplary teeth in row 1 may be offset from one rib in adjacent row 2, either completely out of phase or partially out of phase with the ribs in the adjacent row. As shown, the teeth are completely out of phase from one row 1 to row 2. The positive rib teeth are spaced apart from the separator longitudinal pitch (pitch Tooth ) may be spaced apart by about 3.0 mm to about 6.0 mm, with a typical spacing being about 4.5 mm.

[0073] With continued reference to FIGS. 9A and 9B, the exemplary negative ribs are shown as being substantially parallel to the width direction cmd of the separator 300. However, they may alternatively be substantially parallel to the machine direction md. The exemplary negative ribs shown are shown as being solid and substantially straight. However, they may alternatively be serrated, generally similar to the positive ribs. The negative ribs may be spaced apart (spacing) at a distance of about 10 μm to about 10.0 mm. NegRib ), with a preferred spacing of between about 700 μm and about 800 μm, and a more preferred nominal pitch of about 740 μm. NegRib ) may be from about 10 μm to about 2.0 mm.

[0074] It should be noted that the positive ribs may alternatively be positioned in the exemplary battery to contact the negative plates. Similarly, the negative ribs may alternatively be positioned in the exemplary battery to contact the positive plates. It should further be noted that both the positive and / or negative ribs may be configured similarly to the positive ribs shown in Figures 9A and 9B. Additionally, the positive and negative ribs may both be substantially aligned lengthwise, widthwise, or one lengthwise and the other widthwise.

[0075] The following table 1 shows the dimensions of 162mm x 162mm (262cm 2 The table details the rib count and surface contact area percentage for four separators (one exemplary inventive separator and three control separators) that are 100% sintered. The exemplary inventive separator has 43 toothed ribs that are uniformly spaced across the width of the separator in the width direction. The teeth of the positive electrode side ribs in the exemplary inventive separator are 262 cm2 at the positive electrode. 2 The details of the control separators are further detailed in Table 1. It is understood that control separators No. 1, No. 2, and No. 3 are representative of commercially available separators for currently used flooded lead-acid batteries that are generally currently available in the marketplace.

[0076] [Table 1]

[0077] As described, the inventors have found that maximizing the number of contact points while simultaneously minimizing the contact area achieves the goal of increasing separator resiliency while keeping electrical resistance under control. Additionally, the tine design helps facilitate acid mixing by taking advantage of any motion to which the battery may be subjected. The tines of the separator ribs may be spaced from about 2.5 mm to about 6.0 mm from the nearest adjacent tines. The inventors have found that a preferred, non-limiting distance is about 4.2 mm between adjacent tines. Also, tines that are offset from adjacent rows that are completely out of phase help facilitate acid mixing. The inventors have also found that the base portion helps to strengthen the backweb sufficiently to impart resilience to NAM swelling.

[0078] 10A and 10B, an exemplary electrode surface is shown with areas supported and unsupported from the inventive separator (not shown). FIG. 10A shows a substantial majority of the electrode surface, while FIG. 10B shows a close-up detailed view of it. As can be seen in FIG. 10B, points A, B, and C are shown for various points on the rib or rib tines, along with the radius of the unsupported distance around them (i.e., the distance from one supported point to the nearest adjacent supported point). This unsupported distance may be from about 2.5 mm to about 6.0 mm, as described herein above.

[0079] In certain exemplary embodiments, the positive electrode rib may have a base portion (rib base in FIGS. 9A and 9B). The portion, if present, may have an average base height of about 5 μm to about 200 μm. For example, the average base height may be about 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, or 200 μm or more. Additionally, the portion, if present, may have an average base width that is about 0.0 μm to about 50 μm wider than the tine width. For example, the average base width may be about 0.0 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm or more wider than the tine width.

[0080] In certain exemplary embodiments, the positive electrode side ribs may be teeth or tooth-like ribs. These, when present, have an average tip length (tip L) of about 50 μm to about 1.0 mm. Tooth For example, the average tip lengths may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or more. Alternatively, they may be 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less.

[0081] In some preferred embodiments, at least a portion of the teeth or tooth ribs have an average tooth base length "base L" of about 50 μm to about 1.0 mm. Tooth For example, the average tine base length may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be approximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less.

[0082] In some preferred embodiments, at least a portion of the teeth or tooth ribs have an average height (the height of the base portion and the height of the teeth combined) of about 50 μm to about 1.0 mm. PosRib For example, the average height may be approximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. Alternatively, they may be approximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less.

[0083] In some preferred embodiments, at least a portion of the teeth or ribs may have an average center-to-center pitch within a longitudinal column of between about 100 μm and about 50 mm. For example, the average center-to-center pitch may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or more, in similar increments up to 50 mm. Alternatively, they may be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm or less, in similar increments up to 50 mm. Also, adjacent columns of teeth or ribs may be similarly positioned in the same longitudinal or offset positions. In an offset configuration, adjacent teeth or tooth ribs are disposed at different longitudinal positions.

[0084] In some select preferred embodiments, at least a portion of the teeth or tooth ribs may have an average height to base width ratio of about 0.1:1.0 to about 500:1.0. For example, the average height to base width ratio may be about 0.1:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1, 450:1.0, or 500:1.0. Alternatively, the average height to base width ratio may be less than or equal to approximately 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, or 0.1:1.0.

[0085] In some preferred embodiments, at least a portion of the teeth or tooth ribs can have an average base width to tip width ratio of about 1,000:1.0 to about 0.1:1.0. For example, the average base width to tip width ratio can be about 0.1:1.0, 1.0:1.0, 2:1.0, 3:1.0, 4:1.0, 5:1.0, 6:1.0, 7:1.0, 8:1.0, 9:1.0, 10:1.0, 15:1.0, 20:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 20 It may be 0:1.0, 250:1.0, 300:1.0, 350:1.0, 450:1.0, 500:1.0, 550:1.0, 600:1.0, 650:1.0, 700:1.0, 750:1.0, 800:1.0, 850:1.0, 900:1.0, 950:1.0, or 1,000:1.0. Alternatively, the average base width to tip width ratio is approximately 1,000:1.0, 950:1.0, 900:1.0, 850:1.0, 800:1.0, 750:1.0, 700:1.0, 650:1.0, 600:1.0, 550:1.0, 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0 , 250:1.0, 200:1.0, 150:1.0, 100:1.0, 50:1.0, 25:1.0, 20:1.0, 15:1.0, 10:1.0, 9:1.0, 8:1.0, 7:1.0, 6:1.0, 5:1.0, 4:1.0, 3:1.0, 2:1.0, 1.0:1.0, or 0.1:1.0 or less.

[0086] Backweb Thickness In some embodiments, the porous separator membrane can have a backweb thickness of about 50 μm to about 1.0 mm. For example, the backweb thickness can be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. In other exemplary embodiments, the backweb thickness can be about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm or less. In certain embodiments, very thin flat backweb thicknesses of 50 μm or less are provided, for example, between about 10 μm and about 50 μm thick.

[0087] The total thickness of an exemplary separator (backweb thickness and height of positive and negative side ribs) typically ranges from about 250 μm to about 4.0 mm. The total thickness of a separator used in an automatic start / stop battery is typically about 250 μm to about 1.0 mm. The total thickness of a separator used in an industrial traction start / stop battery is typically about 1.0 mm to about 4.0 mm.

[0088] composition In certain exemplary embodiments, the improved separator may include a porous membrane made from: a natural or synthetic substrate; processed plasticizers; fillers; natural or synthetic rubber(s) or latex, and one or more other additives and / or coatings, and the like.

[0089] Base material In certain embodiments, exemplary natural or synthetic substrates may include: polymers; thermoplastic polymers; phenolic resins; natural or synthetic rubber; synthetic wood pulp; lignin; glass fibers; synthetic fibers; cellulose fibers; and any combination thereof. In certain preferred embodiments, the exemplary separator may be a porous membrane made of a thermoplastic polymer. Exemplary thermoplastic polymers may include, in principle, any acid-resistant thermoplastic material suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers may include polyvinyls and polyolefins. In certain embodiments, polyvinyls may include, for example, polyvinyl chloride ("PVC"). In certain preferred embodiments, polyolefins may include, for example, polyethylene, polypropylene, ethylene-butene copolymers, and any combination thereof, preferably polyethylene. In certain embodiments, exemplary natural or synthetic rubbers may include, for example, latex, non-crosslinked or crosslinked rubber, crumb rubber or shaved rubber, and any combination thereof.

[0090] It has also been observed that when antimony (Sb) is present in the NAM and / or negative electrode, NAM swelling is reduced. Thus, there may be an antimony coating in the separator or an antimony additive in the separator composition.

[0091] Polyolefin In certain embodiments, the porous membrane layer preferably comprises a polyolefin, specifically a polyethylene. Preferably, the polyethylene is a high molecular weight polyethylene ("HMWPE"), (e.g., a polyethylene having a molecular weight of at least 600,000). Even more preferably, the polyethylene is an ultra-high molecular weight polyethylene ("UHMWPE"). Exemplary UHMWPE may 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, as measured by viscosity measurements and calculated by the Margolies equation. Furthermore, exemplary UHMWPE may have a standard load melt index of substantially zero (0), as measured as specified in ASTM D 1238 (condition E) using a standard load of 2,160 g. Also, the exemplary UHMWPE may have a viscosity number, as determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130° C., of 600 ml / g or more, preferably 1,000 ml / g or more, more preferably 2,000 ml / g or more, and most preferably 3,000 ml / g or more.

[0092] Rubber The novel separator disclosed herein may contain latex and / or rubber. As used herein, rubber describes rubber, latex, natural rubber, synthetic rubber, crosslinked or uncrosslinked rubber, cured or uncured rubber, crumb rubber or shaved rubber, or mixtures thereof. Exemplary natural rubbers may include one or more polyisoprene blends, which are commercially available from a variety of sources. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber and silicone rubber and copolymer rubbers, such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber ("EPM" and "EPDM"), and ethylene / vinyl acetate rubber. The rubber may be crosslinked or uncrosslinked; in certain preferred embodiments, the rubber is uncrosslinked. In certain embodiments, the rubber may be a blend of crosslinked and non-crosslinked rubbers.

[0093] Plasticizer In certain embodiments, exemplary processing plasticizers can include processing oils, petroleum oils, paraffinic mineral oils, mineral oils, and any combination thereof.

[0094] Filler The separator may contain a filler with high structural morphology. Exemplary fillers include: silica, dry fine 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 increased surface area. The filler may have a high surface area, for example, greater than 100m2 / g, 110m2 / g, 120m2 / g, 130m2 / g, 140m2 / g, 150m2 / g, 160m2 / g, 170m2 / g, 180m2 / g, 190m2 / g, 200m2 / g, 210m2 / g, 220m2 / g, 230m2 / g, 240m2 / g, or 250m2 / g. In some embodiments, the filler (e.g., silica) may have a surface area of ​​100-300 m2 / g, 125-275 m2 / g, 150-250 m2 / g, or preferably 170-220 m2 / g. Surface area may be evaluated using a TriStar 3000™ for multipoint BET nitrogen surface area. High structural morphology allows the filler to retain additional oil during the manufacturing process. For example, fillers with high structural morphology have high levels of oil absorption, e.g., 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 (e.g., silica) may have an oil absorption of 200-500 ml / 100g, 200-400 ml / 100g, 225-375 ml / 100g, 225-350 ml / 100g, 225-325 ml / 100g, preferably 250-300 ml / 100g. In some cases, a silica filler having an oil absorption of 266 ml / 100g is used. Such a silica filler has a water content of 5.1%, a BET surface area of ​​178 m2 / g, an average particle size of 23 μm, a sieve residue of 0.1% at 230 mesh, and a bulk density of 135 g / L.

[0095] Silica, which has a relatively high level of oil absorption and a relatively high level of affinity for plasticizers (e.g., mineral oil), is desirably dispersible in a mixture of polyolefins (e.g., polyethylene) and plasticizers when forming an exemplary lead-acid battery separator of the type shown herein. Heretofore, some separators have suffered from poor dispersibility caused by silica agglomeration when using high amounts of silica to make such separators or membranes. In at least certain inventive separators shown and described herein, the polyolefin, e.g., polyethylene, forms a shish-kebab structure because there are fewer silica aggregates or agglomerates that inhibit the molecular motion of the polyolefin as the molten polyolefin cools. All of this contributes to improved permeability of the resulting separator membrane, and the formation of the shish-kebab structure or morphology means that separators with lower overall ER are produced while maintaining or even improving mechanical strength.

[0096] In some select embodiments, the filler (e.g., silica) has an average particle size of 25 μm or less, and in some cases, 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm or less. In some cases, the average particle size of the filler particles is 15-25 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 may be within the above size ranges. However, the initial silica used as a raw material may occur as one or more agglomerates and / or aggregates and may have a size of around 200 μm or more.

[0097] In some preferred embodiments, the silica used to make the separator of the present invention has an increased amount or number of surface silanol groups (surface hydroxyl groups) compared to silica fillers previously used to make lead-acid battery separators. For example, silica fillers that may be used according to certain preferred embodiments herein may be such silica fillers that have at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, or at least 35% more silanol and / or hydroxyl surface groups compared to known silica fillers used to make known polyolefin lead-acid battery separators.

[0098] The ratio of silanol groups (Si-OH) to silicon elements (Si), (Si-OH) / Si, can be measured, for example, as follows. 1. Freeze-pulverize a polyolefin porous membrane (certain inventive membranes containing certain oil-absorbing silicas according to the present invention) and use solid-state nuclear magnetic resonance spectroscopy ( 29 Prepare powdered samples for Si-NMR. 2. For powder samples 29 Si-NMR was performed to observe a spectrum containing the spectral intensity of Si directly bonded to hydroxyl groups (spectra: Q2 and Q3) and the spectral intensity of Si directly bonded only to oxygen atoms (spectra: Q4), where the molecular structure of each NMR peak spectrum can be written as follows: Q2: (SiO)2-Si * -(OH)2: has two hydroxyl groups Q3: (SiO)3-Si * -(OH): has one hydroxyl group Q4: (SiO)4-Si * : All Si bonds are SiO Here, Si * is an element that has been verified by NMR observation. 3. Used for observation 29 The conditions for Si-NMR are as follows: ·Equipment: Bruker BioSpin Avance 500 ·Resonance frequency: 99.36MHz Sample size: 250mg NMR tube: 7mφ Observation method: DD / MAS Pulse width: 45° Repeat time: 100 seconds Scans: 800 Magic angle spinning: 5,000Hz Chemical shift reference: -22.43 ppm for silicone rubber 4. Numerically separate the spectrum peaks and calculate the area ratio of each peak belonging to Q2, Q3, and Q4. Then, calculate the molar ratio of hydroxyl groups (-OH) directly bonded to Si based on the ratio. The conditions for numerical peak separation are as follows: Fitting range: -80~-130ppm First peak top: -93ppm in Q2, -101ppm in Q3, and -111ppm in Q4, respectively. First half-width: 400Hz for Q2, 350Hz for Q3, and 450Hz for Q4 respectively. Gaussian function ratio: 80% initially, 70-100% during fitting. 5. Calculate the peak area ratios (sum is 100) of Q2, Q3, and Q4 based on each peak obtained by fitting. The NMR peak areas corresponded to the number of molecules of each silicate bond structure (so that in the NMR peak of Q4, four Si-O-Si bonds exist in the silicate structure; in the NMR peak of Q3, three Si-O-Si bonds exist in the silicate structure while one Si-OH bond exists; in the NMR peak of Q2, two Si-O-Si bonds exist in the silicate structure while two Si-OH bonds exist). Therefore, each number of hydroxyl groups (-OH) in Q2, Q3, and Q4 is multiplied by two (2), one (1), and zero (0), respectively. Sum these three results. The sum represents the molar ratio of hydroxyl groups (-OH) directly bonded to Si.

[0099] In certain embodiments, the silica 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, and in other preferred embodiments at least about 27:100 or more. 29 It may have a molar ratio of OH groups to Si groups as measured by Si-NMR.

[0100] In some select embodiments, the use of the fillers allows for the use of a higher percentage of processing oil during the extrusion step. When the porous structure in the separator is formed, in part, by the removal of oil after extrusion, a higher initial oil absorption results in a higher porosity or higher void volume. Although the processing oil is an integral component of the extrusion step, the oil is a non-conductive component of the separator. Residual oil in the separator protects the separator from oxidation when in contact with the positive electrode. The exact amount of oil in the processing step may be controlled in the manufacture of conventional separators. Generally speaking, conventional separators are manufactured using 50-70% processing oil, in some embodiments 55-65%, in some embodiments 60-65%, and in some embodiments about 62% by weight of processing oil. A reduction of oil below about 59% is known to cause burning due to increased friction against the extruder components. However, an increase in oil much beyond the prescribed amount can cause shrinkage during the drying stage, leading to dimensional instability. While previous attempts to increase the oil content have resulted in pore shrinkage or compression during oil removal, separators prepared as disclosed herein exhibit minimal, if any, shrinkage or compression during oil removal, so porosity can be increased without compromising pore size and dimensional stability, thereby decreasing electrical resistance.

[0101] In certain selected embodiments, the use of the fillers allows for a reduction in the final oil concentration in the finished separator. Because oil is a non-conductor, a reduction in the oil content can increase the ionic conductivity of the separator and help reduce the ER of the separator. Thus, separators with reduced final oil content can have increased efficiency. In certain selected embodiments, separators are provided with a final processed oil content (by weight) of less than 20%, for example, about 14% to 20%, and in some specific embodiments, less than 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, or 5%.

[0102] The fillers may further reduce what is called the hydration layer of electrolyte ions and improve the transport of such ions across the membrane, thereby again lowering the overall electrical resistance or ER of the battery, e.g., enhanced flooded battery or system.

[0103] The filler(s) may contain various species (e.g., polar species, e.g., metals) that facilitate the flow of electrolytes and ions across the separator, which also leads to a reduction in overall electrical resistance when such separators are used in flooded batteries, e.g., reinforced flooded batteries.

[0104] Friability In certain select embodiments, the filler may be alumina, talc, silica, or combinations thereof. In some embodiments, the filler may be precipitated silica, and in some embodiments, the precipitated silica is amorphous silica. In some embodiments, it is preferred to use aggregates and / or agglomerates of silica, which allow fine dispersion of the filler throughout the separator, thereby reducing bending and electrical resistance. In certain preferred embodiments, the filler (e.g., silica) is characterized by a high level of friability. Good friability improves the dispersion of the filler throughout the polymer during extrusion of the porous membrane, improving the porosity and thus the overall ionic conductivity through the separator.

[0105] Friability can be measured as the possibility, tendency or propensity of silica particles or materials (aggregates or agglomerates) to break into smaller size, more disperse particles, pieces or components. The new inventive silica is more friable (broken into smaller pieces after 30 seconds and 60 seconds of sonication) than standard silica. For example, as shown in Figure 11, the new inventive silica may have a 50% volume particle size of 24.90 μm at 0 seconds of sonication, 5.17 μm at 30 seconds, and 0.49 μm at 60 seconds. Thus, there is a size (diameter) reduction of more than 50% at 30 seconds of sonication of 50% volume of silica particles, and a size (diameter) reduction of more than 75% at 60 seconds. Thus, one possibly more preferred definition of "high friability" may be a reduction in the average size (diameter) of silica particles at 30 seconds of sonication (in the treatment of a resin-silica mixture to form a membrane) of at least 50% and a reduction in the average size (diameter) of silica particles at 60 seconds of sonication. At least in certain embodiments, it may be preferred to use a more friable silica, and even more preferred to use a silica that is friable and multimodal in its friability, e.g., bimodal or trimodal. For example, a conventional standard silica may be seen as unimodal in its friability or particle size distribution, while the new silica of the present invention is seen as more friable and bimodal (two peaks) at 30 seconds of sonication and trimodal (three peaks) at 60 seconds of sonication. Such friability and multimodal particle size silica(s) may impart improved membrane and separator properties.

[0106] The use of a filler having one or more of the above characteristics allows the production of a separator with a higher final porosity. The separators disclosed herein may have a final porosity of greater than 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%. Porosity may be measured using a gas adsorption method. Porosity may be measured by BS-TE-2060.

[0107] In some select embodiments, the porous separator can have a greater percentage of larger pores while maintaining an average pore size of about 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, or 0.1 μm or less.

[0108] According to at least one embodiment, the separator is made of polyethylene, e.g., ultra-high molecular weight polyethylene ("UHMWPE"), mixed with processing oil and fillers, as well as any desired additives. According to at least one other embodiment, the separator is made of ultra-high molecular weight polyethylene (UHMWPE) mixed with processing oil and talc. According to at least one other embodiment, the separator is made of UHMWPE mixed with processing oil and silica, e.g., precipitated silica, e.g., amorphous precipitated silica. The additives may then be applied to the separator via one or more of the techniques described above.

[0109] Besides reduced electrical resistance and increased cold cranking amps, the preferred separators are also designed to provide other benefits. For assembly, the separators pass through processing equipment more easily and are therefore more efficiently manufactured. To prevent short circuits during high speed assembly and later in life, the separators have superior puncture strength and oxidation resistance when compared to standard PE separators. Combined with reduced electrical resistance and increased cold cranking amps, battery manufacturers are likely to see improved and sustained electrical performance in batteries with these new separators.

[0110] Conductive Layer In certain embodiments, the separator may contain a performance enhancing additive in the form of a nucleating additive and / or a coating. The nucleating additive may preferably be stable in the battery electrolyte and may be further dispersed within the electrolyte.

[0111] The inventors hypothesize that smaller lead sulfate crystals will go back into solution more easily compared to larger crystals when the battery is charged. Providing nucleation sites is supposed to give the crystals an initiation point to form. Furthermore, multiple nucleation sites can provide multiple crystal formation sites, allowing the total amount of lead sulfate to be spread out among multiple smaller crystals as opposed to fewer larger crystals. These smaller crystals will go back into solution more easily during the battery charging cycle, thereby preventing dendrite growth. The inventors have identified various nucleation additives in the separator, such as carbon and barium sulfate (BaSO4), as exemplary means of providing these nucleation sites. In addition to providing nucleation sites, carbon can also increase battery charge acceptance and increase battery capacity.

[0112] Another advantage that carbon offers is increased charge acceptance. One hypothesis we propose is that the highly conductive carbon particles provide an electronic conduction path, thus improving the utilization of the active material. Another hypothesis we propose is that the carbon increases the capacitance of the separator and therefore the entire battery system.

[0113] Exemplary forms of the nucleating additive and / or coating may be or contain carbon, such as carbon, conductive carbon, graphite, synthetic graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, ketjen black, carbon fiber, carbon filament, carbon nanotube, open cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, and combinations thereof. In addition to these many forms of carbon, the nucleating additive and / or coating may also include or contain barium sulfate (BaSO4), either alone or in combination with carbon.

[0114] The nucleation coating may be applied to the finished separator by means such as slurry coating, slot die coating, spray coating, curtain coating, inkjet printing, screen printing, or vacuum deposition or chemical vapor deposition ("CVD"). The additive and / or coating may also be provided as a carbon paper, either woven or non-woven, and may be disposed between and in intimate contact with the separator and electrode(s).

[0115] The nucleating additive and / or coating may be in the separator, or one or both electrode-facing surfaces of the separator. Typically, a coating or layer of nucleating additive may only be on the negative electrode-facing surface. However, it may also be on the positive electrode-facing surface, or on both surfaces.

[0116] In certain embodiments, the nucleating additive may be added to the extrusion mix of the substrate and extruded with the separator or co-extruded as a layer in the separator. The nucleating additive may replace a portion of the silica filler when included in the extrusion mix, as much as 5% to 75% by weight. For example, the nucleating additive may be approximately 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or approximately 75% by weight. In other exemplary embodiments, the nucleating additive may be approximately 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or approximately 5% by weight or less.

[0117] The conductive layer may be disposed on the exemplary battery separator. The conductive layer may be preferably adapted to contact the battery's positive electrode. The conductive layer may be for providing a new current path to and from the positive electrode. The conductive layer may be made of any conductive material, including, but not limited to, alumina, lead, gold, antimony, arsenic, zinc, barium, beryllium, lithium, magnesium, nickel, aluminum, silver, tin, and combinations thereof, or carbon fiber, graphite, carbon, carbon and zinc, carbon nanotubes, buckminsterfullerenes (or buckyballs), and combinations thereof. The carbon nanotubes or buckyballs may be dispersed in a medium including a binder and applied to the battery separator. The conductive layer may be made of any conductive material that is more corrosion resistant than the positive electrode conductor, thus allowing the conductive layer to function as a positive electrode conductor when the positive electrode conductor's conductive ability is degraded. The conductive layer may be a lead-based alloy with 0.8% to 1.17% tin and greater than zero (0) to 0.015% silver. The conductive layer may be a lead-based alloy with 0.02% to 0.06% calcium, 0.3% to 3% tin, and 0.01% to 0.05% silver. The conductive layer may be made in any form, including but not limited to, strips, screens, foils, threads, wires, coatings, and the like, or combinations thereof. The conductive layer may be of any thickness, for example, approximately 3 μm thick. The conductive layer may be disposed on the battery separator by any means, including but not limited to, adhesive, hot melt, painting, and the like. The conductive layer may be as described in U.S. Pat. No. 9,564,623, the entirety of which is incorporated herein by reference.

[0118] Electrical resistance In certain selected embodiments, the disclosed separators have reduced electrical resistivity, for example, less than about 200 mΩ·cm 2 , 180mΩ·cm 2 , 160mΩ·cm 2 , 140mΩ·cm 2 , 120mΩ·cm 2 , 100mΩ·cm 2 , 80mΩ·cm2 , 60mΩ·cm 2 , 50mΩ·cm 2 , 40mΩ·cm 2 , 30mΩ·cm 2 , or 20 mΩ cm 2 In various embodiments, the separators described herein exhibit an ER reduction of about 20% or more compared to known separators of the same thickness. For example, known separators have an ER reduction of 60 mΩ·cm 2 so that the separator according to the invention at the same thickness has an ER value of about 48 mΩ·cm 2 has an ER value of less than

[0119] To test a sample separator for ER test evaluation according to the present invention, it must first be prepared. For this purpose, the sample separator is preferably immersed in a bath of demineralized water, the water is then boiled and the separator is then removed after 10 minutes in the boiling demineralized water bath. After removal, the excess water is shaken off the separator and then placed in a bath of sulfuric acid having a specific gravity of 1.280 at 27°C ± 1°C. The separator is left in the sulfuric acid bath for 20 minutes. The separator is then ready to be tested for electrical resistance.

[0120] Oxidative Stability In certain selected embodiments, the exemplary separator may be characterized by improved and higher oxidation resistance. The oxidation resistance is measured in the elongation of a sample separator specimen in the width direction after long-term exposure to the environment in a lead-acid battery, including acid electrolyte and temperature fluctuations. For example, the exemplary separator may have an elongation at 40 hours of approximately 100% or more, 150% or more, 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more. In certain embodiments, the exemplary separator may have favorable oxidation resistance or an elongation at 40 hours of approximately 100% or more. Also, the exemplary separator may have an elongation at 20 hours of approximately 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more. In certain embodiments, the exemplary separator may have favorable oxidation resistance or an elongation at 20 hours of approximately 200% or greater.

[0121] To test the sample for oxidation resistance, an exemplary separator sample specimen 1200 is first cut into the shape generally described in Figure 12 A. The sample 1200 is then placed into a sample holder 1220 generally shown in Figures 12B and 12C.

[0122] The first set of samples is tested dry at time=0 hours for percent elongation at break. The elongation is based on a distance of 50±2 mm measured from points A and B in Figure 12A. For example, if points A and B are stretched a distance of 300% upon sample break, the final distance between A and B is 150±6 mm.

[0123] The elongation test is designed to simulate long term exposure to electrolyte in a cycling battery for a shortened period of time. The sample 1200 is first fully submerged in isopropanol, drained, and then submerged in water for 1-2 seconds. The sample is then submerged in the electrolyte. The solution is prepared by sequentially adding 360 ml of 1.28 specific gravity sulfuric acid, 35 ml of 1.84 specific gravity sulfuric acid, and then 105 ml of 35% hydrogen peroxide. The solution is kept at 80°C and the sample is immersed in the solution for an extended period of time. The sample may be tested for elongation at prescribed time intervals, e.g., 20 hours, 40 hours, 60 hours, 80 hours, etc. To test at these intervals, the sample 1200 is removed from the 80°C electrolyte bath and placed under tepid running water until the acid is removed. The elongation can then be tested.

[0124] According to at least selected embodiments, the present disclosure or invention is directed to improved battery separators, low ER or high conductivity separators, improved lead-acid batteries, e.g., flooded lead-acid batteries, high conductivity batteries, and / or improved vehicles including such batteries, and / or methods of making or using such separators or batteries, and / or combinations thereof. According to at least certain embodiments, the present disclosure or invention is directed to improved lead-acid batteries incorporating the improved separators and exhibiting increased conductivity.

[0125] The exemplary separator may also be evaluated for oxidation resistance after comprehensive life testing, such as the SAE-J2801-Comprehensive Life Test, for a 12V automotive battery.

[0126] Puncture resistance In certain selected embodiments, the exemplary separator may be characterized by increased puncture resistance, such as puncture resistance of about 9N or more, 9.5N or more, 10N or more, 10.5N or more, 11N or more, 11.5N or more, 12N or more, 12.5N or more, 13N or more, 13.5N or more, 14N or more, 14.5N or more, 15N or more, 15.5N or more, 16N or more, 16.5N or more, 17N or more, 17.5N or more, 18N or more, 18.5N or more, 19N or more, 19.5N or more, or 20N or more. In certain embodiments, the exemplary separator may be preferably defined by a puncture resistance of about 9N to about 20N or more, or more preferably about 11N to about 20N or more.

[0127] Puncture resistance may be measured as the force required to puncture a porous membrane utilizing tip 1300, generally shown in FIG. 13. The puncture base on which the porous membrane is supported while tip 1300 punctures the membrane may be generally described as a base having a linear hole 6.5 mm in diameter with a depth of 10 mm. The tip's travel limit may be approximately 4 mm to approximately 8 mm below the puncture base surface. The puncture tip 1300 moves linearly into the membrane at a speed of approximately 5 mm / s.

[0128] Additives / Surfactants In certain embodiments, the exemplary separator may contain one or more performance enhancing additives and / or coatings added to the separator or porous membrane. The performance enhancing additives and / or coatings may be surfactants, wetting agents, colorants, antistatic additives and / or coatings, antimony suppression additives and / or coatings, UV-protection additives and / or coatings, antioxidants, and the like, and combinations thereof. In certain embodiments, the additives and / or coating surfactants may be ionic or non-ionic surfactants, or combinations thereof.

[0129] Such performance enhancing additives and / or coatings have been found to reduce hydrogen (H2) evolution and therefore reduce water loss. Such reduced water loss helps to mitigate grid corrosion. The inventors have noted that excessive grid corrosion tends to exacerbate grid warping.

[0130] Certain suitable surfactants may have an HLB value of less than 6, preferably less than 3. The combination of certain suitable surfactants with the inventive separator described herein may result in an even further improved separator when used in a lead-acid battery, which results in reduced water loss, reduced antimony poisoning, improved cycling, reduced float current, reduced float potential, etc., or any combination thereof, for such lead-acid batteries. Suitable surfactants include surfactants such as salts of alkyl sulfates; alkylaryl sulfonate salts; alkylphenol-alkylene oxide adducts; soaps; alkyl-naphthalene-sulfonate salts; one or more sulfosuccinates, such as anionic sulfosuccinates; dialkyl esters of sulfosuccinate salts; amino compounds (primary, secondary, tertiary or quaternary amines); block copolymers of ethylene oxide and propylene oxide; various polyethylene oxides; and salts of mono- and dialkyl phosphate esters. Additives can include nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglucosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters, and sucrose esters of fatty acids.

[0131] In certain embodiments, the additive is a compound of formula (I) [ka] During the ceremony: R is a linear or non-aromatic hydrocarbon radical having 10 to 4200, preferably 13 to 4200, carbon atoms, optionally interrupted by oxygen atoms;

[0132] [ka]

[0133] and preferably H, where k=1 or 2; M is an alkali metal or alkaline earth metal ion, H + or NH 4+ where all variables M are simultaneously H + It does not mean; n=0 or 1; m = 0 or an integer between 10 and 1400; x=1 or 2; It may be represented by:

[0134] The ratio of oxygen atoms to carbon atoms in the compounds according to formula (I) ranges from 1:1.5 to 1:30, and m and n may not simultaneously be 0. However, preferably, only one of the variables n and m is different from 0.

[0135] A non-aromatic hydrocarbon radical means a radical that does not contain or represents an aromatic group. The hydrocarbon radical may be interrupted by oxygen atoms (i.e., it contains one or more ether groups).

[0136] R is preferably a linear or branched aliphatic hydrocarbon radical, which may be interrupted by an oxygen atom. Saturated non-bridged hydrocarbon radicals are very particularly preferred. However, as described above, R may, in certain embodiments, contain an aromatic ring.

[0137] Through the use of the compounds of formula (I) for the preparation of battery separators, these can be effectively protected against oxidative breakdown.

[0138] Formula (I) During the ceremony: R is a hydrocarbon radical having 10 to 180, preferably 12 to 75, very particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20, very particularly preferably 1 to 8 oxygen atoms, particularly preferably a hydrocarbon radical of the formula R 2 -[(OC2H4) p (OC3H6) q ]- During the ceremony: ·R 2 is an alkyl radical having 10 to 30 carbon atoms, preferably having 12 to 25, particularly preferably having 14 to 20 carbon atoms, R 2 may be linear or non-linear, for example with aromatic rings; P is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4; q is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4; Particularly preferred are compounds in which the sum of p and q is 0 to 10, in particular 0 to 4; is a hydrocarbon radical; n=1; m=0 A battery separator containing a compound according to the present invention is preferred.

[0139] formula R 2 -[(OC2H4) p (OC3H6) q ]- should be understood to include those compounds in which the sequence of the radicals in the brackets differs from that shown. For example, compounds in which the radical in the brackets is formed by alternating (OC2H4) and (OC3H6) groups are preferred according to the invention.

[0140] R 2Additives in which is a linear or branched alkyl radical having 10 to 20, preferably 14 to 18, carbon atoms have proven to be particularly advantageous. OC2H4 preferably stands for OCH2CH2, OC3H6, OCH(CH3)2 and / or OCH2CH2CH3.

[0141] As preferred additives, mention may be made in particular of alcohols (p=q=0; m=0), with primary alcohols being particularly preferred, fatty alcohol ethoxylates (p=1-4, q=0), fatty alcohol propoxylates (p=0; q=1-4) and fatty alcohol alkoxylates (p=1-2; q=1-4), with the ethoxylates of primary alcohols being preferred. Fatty alcohol alkoxylates are accessible, for example, through the reaction of the corresponding alcohols with ethylene oxide or propylene oxide.

[0142] Additives of the type m=0, which are not soluble or only sparingly soluble in water and sulfuric acid, have proven to be particularly advantageous.

[0143] Formula (I): In the formula: R is an alkane radical having 20 to 4200, preferably 50 to 750 and very particularly preferably 80 to 225 carbon atoms; M is an alkali metal or alkaline earth metal ion, H + or NH 4+ and in particular alkali metal ions, e.g., Li + , Na + and K. + or H + where all variables M are simultaneously H + It does not mean; n=0; m is an integer from 10 to 1400; x=1 or 2; Also preferred is an additive comprising a compound according to

[0144] Salt Additives In certain embodiments, suitable additives include, in particular, polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers, whose acid groups are at least partially neutralized, for example, preferably by 40%, particularly preferably by 80%. The percentage refers to the number of acid groups. Very particularly preferred is poly(meth)acrylic acid, which is present entirely in salt form. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn and ammonium (NR4, where R is either hydrogen or a carbon functional group). Poly(meth)acrylic acids include polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acids, in particular, have an average molar mass M of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol and very particularly preferably 1,000 to 4,000 g / mol. w Preferred is a polyacrylic acid having the formula: The molecular weight of the poly(meth)acrylic acid polymers and copolymers is ascertained by measuring the viscosity (Fikentscher's constant) of a 1% aqueous solution of the polymer, neutralized with sodium hydroxide solution.

[0145] Copolymers of (meth)acrylic acid are also suitable, in particular copolymers which, in addition to (meth)acrylic acid, contain ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate as comonomers. Preference is given to copolymers which contain at least 40% by weight and preferably at least 80% by weight of (meth)acrylic acid monomer; the percentages are based on the acid form of the monomer or polymer.

[0146] Alkali metal and alkaline earth metal hydroxides, such as potassium hydroxide and especially sodium hydroxide, are particularly preferred for neutralizing polyacrylic acid polymers and copolymers. Coatings and / or additives for improving the separator may also include, for example, metal alkoxides, where the metals may be, for example (not intended to be limiting), only Zn, Na, or Al, for example only sodium ethoxide.

[0147] In some embodiments, the porous polyolefin membrane may include a coating on one or both sides of such layer. Such coating may include surfactants or other materials. In some embodiments, the coating may include one or more materials described, for example, in U.S. Patent Application Publication No. 2012 / 0094183, which is incorporated herein by reference. Such coating may extend battery life with less grid corrosion, for example, by reducing the overcharge voltage of the battery system, and may also prevent drying and / or moisture loss.

[0148] ratio In certain select embodiments, the membrane may be prepared by combining, by weight, about 5-15% polymer, in some cases about 10% polymer (e.g., polyethylene), about 10-75% filler (e.g., silica), in some cases about 30% filler, and about 10-85% processing oil, in some cases about 60% processing oil. In other embodiments, the filler content is reduced and the oil content is higher, for example, about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or greater than 70% by weight. The filler:polymer ratio (by weight) may be about (or may be approximately within these specific ranges), for example, 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1. 4.5:1, 5.0:1, 5.5:1, or 6:1. The filler:polymer ratio (by weight) may 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 rubber, filler, oil, and polymer are all balanced with respect to runnability and the desired separator properties, such as electrical resistivity, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flexural strength, and the like.

[0149] According to at least one embodiment, the porous membrane may include UHMWPE mixed with processing oil and precipitated silica. According to at least one embodiment, the porous membrane may include UHMWPE mixed with processing oil, additives, and precipitated silica. The mixture may include small amounts of other additives or agents as is common in the separator field (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, etc., and any combination thereof). In certain cases, the porous polymer layer may be a homogeneous mixture of 8-100% by volume polyolefin, 0-40% by volume plasticizer, and 0-92% by volume inert filler material. A preferred plasticizer is petroleum. Plasticizers are useful for imparting porosity to battery separators because they are the easiest component to remove from the polymer-filler-plasticizer composition by solvent extraction and drying.

[0150] In certain embodiments, the porous membranes disclosed herein may include latex and / or rubber, which may be natural rubber, synthetic rubber, or a mixture thereof. Natural rubber may include one or more polyisoprene blends, which are commercially available from various sources. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonyl polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber and copolymer rubber, such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber may be crosslinked or non-crosslinked; in certain preferred embodiments, the rubber is non-crosslinked. In certain embodiments, the rubber may be a blend of crosslinked and non-crosslinked rubber. The rubber may be present in the separator in an amount of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight based on the final separator weight (weight of the polyolefin separator sheet or layer containing rubber and / or latex). In certain embodiments, the rubber may be present in an amount of about 1-6%, about 3-6%, about 3%, about 6% by weight. The porous membrane may have a filler to polymer and rubber weight ratio (filler:polymer and rubber) of about 2.6:1.0. The amounts of rubber, filler, oil, and polymer are all balanced with respect to runnability and desired separator properties, such as electrical resistivity, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flexural strength, etc.

[0151] Porous membranes made according to the present invention, including polyethylene and fillers (e.g., silica), typically have residual oil; in some embodiments, such residual oil is about 0.5% up to about 40% of the total weight of the separator membrane (in some cases, about 10-40% of the total weight of the separator membrane, in some cases, about 20-40% of the total weight). In certain select embodiments herein, some to all of the residual oil in the separator may be replaced by the addition of a performance enhancing additive, such as a surfactant, such as a surfactant with a hydrophilic-lipophilic balance ("HLB") of less than 6, or, for example, a non-ionic surfactant. For example, the performance enhancing additive, such as a surfactant, such as a non-ionic surfactant, may partially or completely replace the residual oil in the separator membrane by constituting up to 0.5% up to the amount of residual oil (e.g., up to 20% or 30% or even 40%) of the total weight of the porous separator membrane.

[0152] manufacturing In some embodiments, the exemplary porous membrane may be made by mixing the components in an extruder. For example, about 30% by weight of filler may be mixed in an extruder with about 10% by weight of UHMWPE and about 60% of processing oil. The exemplary porous membrane may be made 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 press or calender stacks or rolls to form a continuous web. A significant amount of processing oil from the web may be extracted by using a solvent, which is followed by removal of the solvent by drying. The web may then be cut into lanes of a predetermined width and then wound onto a roll. Additionally, the press or calender roll may be engraved with various groove patterns to impart ribs, grooves, textured areas, embossments, etc., substantially as described herein.

[0153] Rubber manufacturing In some embodiments, the exemplary porous membrane may be made by mixing the components in an extruder. For example, about 5-15% by weight of a polymer (e.g., polyethylene), about 10-75% by weight of a filler (e.g., silica), about 1-50% by weight of a rubber and / or latex, and about 10-85% by weight of a processing oil may be mixed in the extruder. The exemplary porous membrane may be made 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 press or calendar stacks or rolls to form a continuous web. A significant amount of the processing oil from the web may be extracted by the use of a solvent. The web may then be dried and slit into lanes of a predetermined width and then wound onto a roll. Additionally, the press or calendar roll may be imprinted with various groove patterns to impart ribs, grooves, textured areas, embossments, etc., substantially as described herein. The amounts of rubber, filler, oil, and polymer are all balanced with respect to runnability and the desired separator properties, such as electrical resistivity, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flexural strength, and the like.

[0154] In addition to being added to the extruder component, certain embodiments combine the rubber with the porous membrane after extrusion. For example, the rubber may be coated on one or both sides, preferably the side facing the negative electrode, with a liquid slurry containing rubber and / or latex, optionally silica, and water, and then dried so that a film of this material is formed on the surface of the exemplary porous membrane. For better wettability of this layer, known wetting agents may be added to the slurry for use in lead-acid batteries. In certain embodiments, the slurry may also contain one or more performance enhancing additives as described herein. After drying, a porous layer and / or film is formed on the surface of the separator, which adheres fairly well to the porous membrane and increases the electrical resistance only slightly, if at all. After being added, the rubber may be further compressed using either a mechanical press or a calender stack or roll. Other possible ways of applying the rubber and / or latex are to apply the rubber and / or latex slurry by dip coating, roller coating, spray coating or curtain coating of the surface to one or more of the separators, or any combination thereof. These processes may occur before or after the processing oil is extracted and before or after the lanes are slit.

[0155] A further embodiment of the present invention involves depositing a rubber onto the membrane by impregnation and drying.

[0156] Manufactured with performance enhancing additives In certain embodiments, performance enhancing additive(s) (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, and the like, and any combination thereof) may also be mixed in the extruder along with the other components. The porous membrane according to the present disclosure may then be extruded into a sheet or web shape and finished in substantially the same manner as described above.

[0157] In certain embodiments, in addition to or alternatively to addition in the extruder, the additive(s) may be applied to the separator porous membrane, for example when finished (for example after the bulk of the processing oil has been extracted and before or after the introduction of the rubber). According to certain preferred embodiments, the additive or a solution of the additive (for example an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for the application of non-thermally stable additives and additives that are soluble in the solvent used to extract the processing oil. Particularly suitable solvents for the additives according to the invention are low molecular weight alcohols, for example methanol and ethanol, and mixtures of these alcohols with water. The application may be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or on both sides. The application may also be carried out during the extraction of the pore former (for example the processing oil) while in the solvent bath. In certain select embodiments, a portion of the performance enhancing additives, such as the surfactant coating or performance enhancing additives (or both), that are added to the extruder before the separator is made may combine with the antimony in the battery system, deactivate it, and / or form a compound with it, and / or drip it into the battery mud rest, and / or prevent it from accumulating on the negative electrode. The surfactant or additive may also be added to the electrolyte, glass mat, battery case, application mat, etc., or combinations thereof.

[0158] In certain embodiments, the additive (e.g., a nonionic surfactant, an anionic surfactant, or a mixture thereof) is present in an amount of at least 0.5 g / m 2 , 1.0g / m 2 , 1.5g / m 2 , 2.0g / m 2 , 2.5g / m 2 , 3.0g / m 2 , 3.5g / m 2 , 4.0g / m 2 , 4.5g / m 2 , 5.0g / m 2 , 5.5g / m 2 , 6.0g / m 2 , 6.5g / m 2, 7.0g / m 2 , 7.5g / m 2 , 8.0g / m 2 , 8.5g / m 2 , 9.0g / m 2 , 9.5g / m 2 Or 10.0 g / m 2 or even up to about 25.0 g / m 2 The additive may be present at a density or add-on level of 0.5 to 15 g / m 2 , 0.5~10g / m 2 , 1.0~10.0g / m 2 , 1.5~10.0g / m 2 , 2.0~10.0g / m 2 , 2.5~10.0g / m 2 , 3.0~10.0g / m 2 , 3.5~10.0g / m 2 , 4.0~10.0g / m 2 , 4.5~10.0g / m 2 , 5.0~10.0g / m 2 , 5.5~10.0g / m 2 , 6.0~10.0g / m 2 , 6.5~10.0g / m 2 , 7.0~10.0g / m 2 , 7.5~10.0g / m 2 , 4.5~7.5g / m 2 , 5.0~10.5g / m 2 , 5.0~11.0g / m 2 , 5.0~12.0g / m 2 , 5.0~15.0g / m 2 , 5.0~16.0g / m 2 , 5.0~17.0g / m 2 , 5.0~18.0g / m 2 , 5.0~19.0g / m 2 , 5.0~20.0g / m 2 , 5.0~21.0g / m 2 , 5.0~22.0g / m 2 , 5.0~23.0g / m 2 , 5.0~24.0g / m 2 , or 5.0 to 25.0 g / m 2The separator may be present at a density or add-on level between 0.1 and 1.

[0159] The application may also be performed by immersing the battery separator in the additive or in a solution of the additive (solvent bath application) and removing the solvent as needed (e.g., by drying). Thus, the application of the additive may be combined with an extraction, which is often applied, for example, during membrane production. Other preferred methods are spraying the surface with the additive, dip-coating, roller-coating, or curtain-coating the surface of the separator with one or more additives.

[0160] In certain embodiments described herein, reduced amounts of ionic, cationic, anionic, or nonionic surfactants are added to the inventive separator. In such cases, desired characteristics may include lower total organic carbon and / or lower volatile organic compounds (due to lower amounts of surfactant) that may produce the desired inventive separator according to such embodiments.

[0161] Combination with fiber mats In certain embodiments, the exemplary separator according to the present disclosure may be combined with one or more other layer(s) (laminated or otherwise), such as a fiber layer or fiber mat having improved wicking properties and / or improved electrolyte wetting or retention properties. The fiber mat may be woven, nonwoven, fleece, mesh, net, single layer, multi-layer (where each layer may have the same, similar or different characteristics as the other layers), composed of synthetic fibers, fleece, or fibers made from glass fibers, or synthetic fibers or mixtures of glass and synthetic fibers or paper, or any combination thereof. The fiber mat may be a single piece or separate strips in each side lane.

[0162] In certain embodiments, the fiber mat (laminated or otherwise) may be used as a carrier for additional materials. The additional materials may include, for example, carbon, BaSO4, rubber and / or latex, optionally silica, water, and / or one or more performance enhancing additives, such as the various additives described herein, or any combination thereof. By way of example, the additional materials may be delivered in the form of a slurry that may then be coated onto one or more surfaces of the fiber mat to form a film or dipped into the fiber mat to impregnate it.

[0163] When the fibrous layer is present, it is preferred that the porous membrane has a larger surface area than the fibrous layer. Therefore, when the porous membrane and the fibrous layer are combined, the fibrous layer does not completely cover the porous layer. At least two opposing edge regions of the membrane layer are preferably left uncovered to provide edges for heat sealing to facilitate optional formation of pockets or envelopes, etc. Such a fibrous mat may have a thickness of at least 100 μm, in some embodiments at least about 200 μm, at least about 250 μm, at least about 300 μm, at least about 400 μm, at least about 500 μm, at least about 600 μm, at least about 700 μm, at least about 800 μm, at least about 900 μm, at least about 1 mm, at least about 2 mm, etc. The laminated separator may then be cut into pieces. In certain embodiments, the fibrous mat is laminated to the ribbed surface of the porous membrane. In certain embodiments, handling and / or assembly advantages are provided to battery manufacturers with the improved separators described herein since they may be supplied in roll and / or cut strip form, and as mentioned above, the improved separators may be stand-alone separator sheets or layers without the addition of one or more fiber mats or the like.

[0164] The fiber mat, when laminated to the porous membrane, may be bonded together by adhesives, heat, ultrasonic welding, compression, etc., or any combination thereof, and the fiber mat may be a PAM or NAM retaining mat.

[0165] Consideration Details of one or more exemplary embodiments, aspects, or objects are set forth in the detailed description and claims set forth below. Other features, objects, and advantages will be apparent from the detailed description and claims set forth below. According to one or more selected embodiments, aspects, or objects, the present disclosure or invention at least addresses, and in some cases goes beyond, the problems, challenges, or needs set forth above.

[0166] According to at least select exemplary embodiments, aspects, or objectives, the present invention at least addresses the above problems or needs and provides new or improved separators, new or improved batteries utilizing the new or improved separators, and new or improved systems utilizing the new or improved batteries. According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to new or improved battery separators, battery cells, batteries, systems, and / or methods of making and / or using such new or improved battery separators, battery cells, batteries, and / or systems.

[0167] According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery having at least an improved construction and rib configuration for reducing or mitigating electrode plate warping and / or the effects of electrode plate warping; reduced occurrence of separator puncture; reduced occurrence of battery electrode shorting; etc.; and / or combinations thereof. According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery that may be characterized by at least one or more of: plate-warp resistance; puncture resistance; oxidation resistance; acid mixing; reduced electrical resistance; improved wettability; improved filler; optimized porosity; optimized tortuosity; reduced thickness; reduced backweb thickness; ribbed; anode side cross ribs; reduced oil content; increased acid diffusion; increased oxidation resistance or improved oxidation stability; optimized porosity; optimized pore tortuosity; improved acid diffusion; etc.; and / or combinations thereof. In accordance with at least certain example embodiments, aspects, or objectives, the present disclosure or invention is directed to an improved separator for lead-acid batteries that may provide at least one or more of: low water loss in batteries and / or battery cells; reduced electrical resistance in batteries and / or battery cells; increased acid mixing in batteries and / or battery cells; reduced acid stratification in batteries and / or battery cells; improved performance in batteries and / or battery cells; increased life in batteries and / or battery cells; reduced failure rates in batteries and / or battery cells; and / or combinations thereof.

[0168] According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to separators and / or improved battery cells and / or batteries utilizing the improved separators, and / or improved systems utilizing the improved battery cells and / or batteries utilizing the improved separators, that overcome at least the problems and / or challenges noted above. For example, and by way of example only, the improved battery cells and / or batteries may be characterized by at least one or more of: improved performance; reduced failure rates; improved life span; reduced plate shorting occurrences; reduced separator puncture occurrences; reduced water loss; reduced float current; improved charge termination current; increased charge acceptance; improved energy throughput; reduced antimony (Sb) poisoning; reduced acid stratification; reduced acid starvation; reduced dendrite formation; reduced internal electrical resistance; improved cold cranking amps ("CCA"), improved uniformity; improved cycle performance; and / or combinations thereof.

[0169] According to at least select example embodiments, aspects, or objectives, the present disclosure or invention is directed to at least new or improved battery separators, warp resistant separators, puncture resistant separators, elastomeric separators, battery cells, batteries, methods involving same, systems using same, vehicles using same, methods of manufacturing same, methods of using same, and combinations thereof.

[0170] In accordance with at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to new or improved battery separators for use in a variety of batteries and / or applications, including an exemplary list of: flat plate batteries; tubular batteries; flooded lead acid batteries; reinforced flooded lead acid batteries ("EFB"); valve regulated lead acid ("VRLA") batteries; deep cycle batteries; gel batteries; absorbent glass mat ("AGM") batteries; inverter batteries; current collector batteries; storage batteries; internal combustion engine batteries; auxiliary batteries; starting-lighting-ignition ("SLI") batteries; idle-start-stop ("ISS") batteries; vehicle batteries; passenger car batteries; automobile batteries; truck batteries; batteries; motorcycle batteries; all-terrain vehicle batteries; marine batteries; aircraft batteries, forklift batteries; golf cart or golf car batteries; hybrid electric vehicle ("HEV") batteries; micro-hybrid vehicle batteries; electric vehicle batteries; electric rickshaw batteries; electric tricycle batteries; electric bicycle batteries; uninterruptible power supply ("UPS") batteries; batteries with high CCA requirements; batteries operating in partial state of charge ("PSoC"); etc; and combinations thereof.

[0171] According to at least selected exemplary embodiments, aspects, or objectives, numerous systems are provided that include the inventive battery incorporating the inventive separator described herein. Exemplary systems may be one or more of: vehicles; UPS; auxiliary power systems; current collector systems; renewable energy current collector systems; wind energy current collector systems; solar energy current collector systems; backup power systems; inverters; and combinations thereof. Further, exemplary vehicles may be one of: automobiles; cars; trucks; forklifts; hybrid vehicles; HEVs; micro-hybrid vehicles; ISS vehicles; electric vehicles; water containers; aircraft; electric rickshaws; electric tricycles; electric bicycles; motorcycles; all-terrain vehicles; golf carts or golf cars; and the like; and combinations thereof.

[0172] In a first exemplary embodiment of the present disclosure or invention, the electrode and separator assembly includes an electrode plate having a grid and an active material thereon. The grid includes at least one grid edge. Furthermore, the active material may be non-uniformly distributed on the grid. In another embodiment, the grid may be thinner than approximately 1.00 mm. In yet another embodiment, the grid may have a non-uniform geometry.

[0173] A porous membrane is disposed adjacent to the electrode plate having a first membrane surface having a first surface edge and a second surface edge and a plurality of ribs extending from the membrane surface;

[0174] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly may be either a positive or negative electrode and includes an electrode plate having a grid and an active material non-uniformly distributed thereon. The grid includes a first grid edge and a second grid edge. The porous membrane is disposed adjacent to the electrode plate. The porous membrane has a first side lane adjacent to the first membrane edge and a second side lane adjacent to the second membrane edge, and a central portion disposed between the first and second side lanes. The porous membrane includes a first membrane surface having a plurality of primary ribs extending from or into the first membrane surface in the central portion, and a first array of secondary ribs disposed in the first side lane and a second array of secondary ribs disposed in the second side lane.

[0175] In one embodiment of the invention, the first grid edge may be disposed in the first side lane and the second grid edge may be disposed in the second side lane. The plurality of primary ribs may have a uniform height and uniform distribution. Meanwhile, either or both of the first array of secondary ribs and the second array of secondary ribs are more densely packed than the plurality of primary ribs. The plurality of primary ribs, the first array of secondary ribs, and / or the second array of secondary ribs may be longitudinally disposed substantially parallel to the length of the porous membrane, or laterally disposed substantially parallel to the width of the porous membrane. Either or both of the first array of secondary ribs and the second array of secondary ribs may be substantially parallel, orthogonal, or angled to the plurality of primary ribs. The porous membrane may have a second membrane surface having a third array of ribs thereon.

[0176] In another aspect of the invention, the grid may be a stamped grid, a cast grid, or an expanded metal grid. Additionally, the grid may be prone to warping. The grid may have a first grid surface and a second grid surface, and the active material may be more highly distributed on the first grid surface compared to the second grid surface. Additionally, the active material may be non-uniformly distributed on the surface of the grid.

[0177] In yet another embodiment, any of the plurality of primary ribs, the first array of secondary ribs, the second array of secondary ribs, and / or the third array of ribs may be one or more of: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs that may extend longitudinally in a substantially longitudinal direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof.

[0178] In certain embodiments, the porous membrane may be one of an envelope, a hybrid envelope, a sleeve separator, a pocket separator, and a wrap separator. The porous membrane may have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesive, and combinations thereof. The porous membrane may be a cut piece.

[0179] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly comprises an electrode plate, which may be either a positive or negative electrode, and has a grid and active material non-uniformly distributed thereon. The porous membrane may comprise a first membrane surface having an array of primary ribs disposed on such first membrane surface and extending from a first membrane edge to a second membrane edge; the array of primary ribs has a uniform height.

[0180] Another aspect of the present invention or disclosure provides a grid having a first grid surface and a second grid surface, and the active material is more highly distributed on the first grid surface compared to the second grid surface. Alternatively, or in addition, the active material may be non-uniformly distributed on the surface of the grid. The grid may be one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid. Also, the grid may be prone to warping. Either the first film surface or the second film surface may be adjacent to an electrode plate.

[0181] In another aspect of the invention or disclosure, the array of primary ribs may be disposed longitudinally and substantially parallel to the length of the porous membrane and may be uniformly or non-uniformly spaced laterally across the width of the porous membrane. The porous membrane may have a second surface from which a second array of ribs extends.

[0182] In another embodiment of the present invention or disclosure, either or both of the primary array of ribs and / or the second array of ribs may be one or more of: solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs that may extend longitudinally in a substantially longitudinal direction of the porous membrane, ribs that may extend laterally in a substantially width direction of the porous membrane, ribs that may extend transversely in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof.

[0183] In one exemplary embodiment, the porous membrane may be one of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator; the envelope, hybrid envelope, sleeve separator, pocket separator, and wrap separator may have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

[0184] In yet another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly may include an electrode plate having a grid and an active material. The grid may have a first grid edge and a second grid edge, and the active material may be non-uniformly distributed on the grid. The porous membrane may further include a first membrane surface having a support structure supporting the first grid edge and the second grid edge. The first grid edge may have at least a first grid corner, and the second grid edge may have at least a second grid corner. The support structure may have a first array of ribs having a uniform height.

[0185] The grid may have a first grid surface and a second grid surface, and the active material may be more highly distributed on the first grid surface compared to the second grid surface. Alternatively, or in addition, the active material may be non-uniformly distributed on the surface of the grid. The grid may be one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid. The electrode plate may be prone to warping.

[0186] In certain exemplary embodiments, the first array of ribs may be uniformly spaced laterally from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane. The first array of ribs may also be uniformly or non-uniformly spaced laterally from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane.

[0187] In other exemplary embodiments of the present disclosure, the first array of ribs may be more densely packed in a first membrane region adjacent a first membrane edge and more densely packed in a second membrane region adjacent a second membrane edge compared to the ribs spaced apart in a central portion of the porous membrane.

[0188] In yet another exemplary aspect of the present disclosure, the first array of ribs may be uniformly or non-uniformly spaced laterally from a first grid edge to a second grid edge, and the first array of ribs may be more densely packed in a first region adjacent the first grid edge and more densely packed in a second region adjacent the second grid edge compared to the ribs spaced apart in a central portion of the grid.

[0189] In yet another aspect of the present disclosure, the support structure may have a fiber mat; the fiber mat may extend from a first grid edge to a second grid edge. The support structure may have a first fiber mat adjacent to the first grid edge and a second fiber mat adjacent to the second grid edge.

[0190] In another exemplary embodiment, the porous membrane can be one of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator; the envelope, hybrid envelope, sleeve separator, pocket separator, and wrap separator can have at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

[0191] In yet another exemplary embodiment of the present disclosure, a lead-acid battery may comprise a separator substantially as described herein. The lead-acid battery may be operated in one of the following states: driving, stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial state of charge, and combinations thereof.

[0192] Exemplary batteries may be one of: a flat plate battery, a flooded lead acid battery, an reinforced flooded lead acid battery ("EFB"), a valve regulated lead acid ("VRLA") battery, a deep cycle battery, a gel battery, an absorbent glass mat ("AGM") battery, a tubular battery, an inverter battery, a vehicle battery, a starting-lighting-ignition ("SLI") vehicle battery, an idle-start-stop ("ISS") vehicle battery, an automobile battery, a truck battery, a marine battery, a motorcycle battery, an all-terrain vehicle battery, a forklift battery, a golf cart battery, a hybrid electric vehicle battery, an electric car battery, an electric rickshaw battery, an electric three-wheeler battery, and an electric bicycle battery;

[0193] In yet another exemplary embodiment, the system may comprise a lead-acid battery as described herein. The system may comprise a vehicle, which may be one of an automobile, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart, a hybrid vehicle, a hybrid electric vehicle, an electric vehicle, an idle-start-stop ("ISS") vehicle, a water container, an electric rickshaw, an electric three-wheeler, and an electric bicycle. Additionally, the system may operate in one of the following states: while driving, while stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial charge state, and combinations thereof. The system may further be one of the following: an uninterruptible power supply, an energy storage system, a power backup system, a renewable energy storage system, and combinations thereof.

[0194] In yet another exemplary embodiment, a method for mitigating grid warpage in an electrode and separator assembly may be provided. The method may provide an electrode plate having a grid susceptible to warping; and position a support structure adjacent to the grid. The support structure may include a battery separator. Additionally, the support structure may include a fiber mat or mesh. The active material may be non-uniformly applied to the grid. The grid may have a perimeter. The support structure may overlap at least a portion of the grid perimeter. The support structure may be provided as a set of ribs extending from a porous membrane having a uniform height. The set of ribs may be longitudinally disposed in a machine direction of the porous membrane, and the set of ribs may be equally spaced in a lateral dimension in a width direction from a first edge of the perimeter to a second edge of the perimeter. Alternatively or in addition, the support structure may include or be a polygonal spacer. Alternatively or in addition, the support structure may include or be a fiber mat. Alternatively, or in addition, the support structure may include or be a first fiber mat and a second fiber mat, the first fiber mat disposed to at least partially overlap a first edge of the periphery; and the second fiber mat disposed to at least partially overlap a second edge of the periphery. The method may further provide for subjecting the electrode and separator assembly to elevated temperatures and / or thermal cycling.

[0195] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention provides a separator whose components and physical attributes and features combine synergistically to address in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a battery using the separator described herein that addresses in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved lead-acid battery separator. In certain preferred exemplary embodiments, the present disclosure or invention provides a system using the battery described herein that addresses in an unexpected manner a heretofore unmet need in the lead-acid battery industry with an improved system utilizing the inventive lead-acid battery utilizing the inventive separator described herein.

[0196] In accordance with at least selected exemplary embodiments, aspects, or objectives, the present invention solves, meets, and / or overcomes at least problems, needs, and / or issues heretofore unsolved, unmet, and / or unaddressed in the current state of the art. In accordance with at least certain objectives, the present invention provides improved separators, improved cells or batteries utilizing the improved separators, and / or improved systems using the improved separators, cells or batteries that overcome at least certain of the problems, issues, or needs set forth above.

[0197] According to at least select exemplary embodiments, aspects, or objectives, the present disclosure or invention may address at least the problems, challenges, or needs set forth above, and / or may provide new or improved separators, warp resistant separators, and / or lead acid battery separators, new or improved cells or batteries utilizing the new or improved separators, and / or new or improved systems utilizing the new or improved separators, cells or batteries. According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to new or improved battery separators, battery cells, batteries, systems, and / or methods of making and / or using such new or improved battery separators, battery cells, batteries, and / or systems.

[0198] Exemplary embodiments of an improved electrode plate and separator assembly (400) for lead-acid batteries, an improved lead-acid cell or battery incorporating the improved assembly, a system or vehicle incorporating the improved assembly (400) and / or battery (100), and related methods are disclosed herein. The electrode plate (200, 201) may have a grid (202) from a stamping, casting, or expanded metal manufacturing process. The grid (202) may have a non-uniform application of active material (203). The separator (300) preferably provides a support structure to withstand or mitigate any plate warping or plate deflection.

[0199] In accordance with at least selected embodiments, the present disclosure or invention is directed to separators, particularly for flooded lead-acid batteries, that reduce or mitigate battery water loss, reduce antimony (Sb) poisoning, reduce electrode plate grid warping or bending or distortion; reduce or mitigate acid deficiency; reduce or mitigate acid stratification; reduce or mitigate dendrite growth; reduce the effects of oxidation; reduce water loss; increase wettability; improve acid diffusion; improve uniformity; and are capable of increasing cold cranking amps, have reduced electrical resistance, etc.; and combinations thereof. Also disclosed herein are methods, systems, and battery separators for improving battery life, reducing battery water loss, reducing battery antimony (Sb) poisoning, reducing or mitigating electrode plate grid warping or bending or distortion, reducing or mitigating acid starvation, reducing or mitigating acid stratification, reducing or mitigating dendrite growth, reducing the effects of oxidation, reducing internal resistance, increasing wettability, improving acid diffusion, improving cold cranking amperage, improving uniformity, etc., and any combination thereof, at least in reinforced flooded lead-acid batteries. According to at least certain embodiments, the present disclosure or invention is directed to improved separators for reinforced flooded lead-acid batteries, including improved constructions for reduced battery water loss and reduced antimony (Sb) poisoning, improved separator grid-warping resistance, improved separator resiliency, and combinations thereof.According to at least certain embodiments, the present disclosure or invention is directed to improved separators for reinforced flooded lead-acid batteries, including improved constructions including cross-linking components, additives or coatings that enhance performance, increased oxidation resistance, amorphous silica, higher oil absorption silica, higher silanol group silica, silica with OH:Si ratios of 21:100 to 35:100, polyolefin microporous membranes containing particle-like fillers in amounts of 40% or more by weight of the membrane and polymer, such as ultra-high molecular weight polyethylene ("UHMWPE"), reduced sheet thickness, reduced caliper, reduced oil content, increased wettability, increased acid diffusion, and the like, as well as any combination thereof.

[0200] According to at least certain embodiments, aspects, or objectives, the present disclosure or invention is directed to or provides new or improved separators for various lead-acid batteries and / or systems. Also, exemplary embodiments disclosed herein are directed to new or improved battery separators, warp resistant separators, battery cells incorporating such separators, batteries incorporating such separators, systems incorporating such separators, and / or methods of making and / or using such separators, new or improved lead-acid batteries, and / or combinations thereof. At least selected embodiments are directed to new or improved separators, batteries, and / or systems that provide improved battery life and / or reduced battery failure in lead-acid batteries, such as those having or operating with stamped plate electrodes, stamped grid electrodes, non-uniform active material electrodes, warped plate electrodes, or plate electrodes that are prone to warping, utilizing such new or improved separators.

[0201] Exemplary embodiments of an improved electrode plate and separator assembly (400) for lead-acid batteries, an improved lead-acid cell or battery incorporating the improved assembly, a system or vehicle incorporating the improved assembly (400) and / or battery (100), and related methods are disclosed herein. The electrode plate (200, 201) may have a grid (202) from a stamping, casting, or expanded metal manufacturing process. The grid (202) may have a non-uniform application of active material (203). The separator (300) preferably provides a support structure to withstand or mitigate any plate warping or plate deflection.

[0202] The above written detailed description of the structures and methods has been presented for illustrative purposes only. Examples are used to disclose exemplary embodiments, including the best mode, and to enable one of ordinary skill in the art to practice the invention, including making and using any device or system, and performing any incorporated methods. These examples are not intended to be exhaustive or to limit the invention to the precise steps and / or forms disclosed, and many modifications and variations are possible in light of the above teachings. The features described herein may be combined in any combination. The steps of the methods described herein may be performed in any order that is physically possible. The patentable scope of the invention is defined by the appended claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims when they have structural elements that do not differ from the literal language of the claims, or when they include equivalent structural elements that have insubstantial differences from the literal language of the claims.

[0203] The present invention may be embodied in other forms without departing from its spirit and essential characteristics, and therefore, reference should be made to the appended claims rather than the above specification as indicating the scope of the present invention. Components that can be used to implement the disclosed methods and systems are disclosed. These and other components are disclosed herein, and it is understood that combinations, subsets, interactions, groups, etc. of these components, when disclosed, are specifically contemplated and described herein for all methods and systems, although specific references to each of these various individual and collective combinations and sequences may not be expressly disclosed. This applies to all aspects of this application, including, but not limited to, steps in the disclosed methods. Thus, when there are various additional steps that can be implemented, it is understood that each of these additional steps can be implemented by any particular embodiment or combination of embodiments of the disclosed methods.

[0204] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of some embodiments of the claims. Any composition(s) and / or method(s) that are functionally equivalent are intended to be within the scope of the appended claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to be within the scope of the appended claims. Furthermore, while only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of compositions and method steps are also intended to be within the scope of the appended claims even if not specifically recited. Thus, although combinations of steps, elements, components, or ingredients may be explicitly mentioned herein or below, other combinations of steps, elements, components, and ingredients are included even if not explicitly described. Except in the examples, or where otherwise stated, all numbers expressing quantities of ingredients, reaction conditions, and the like used in the specification and claims should be understood as at least, and should be interpreted in light of significant digits and ordinary rounding approaches, rather than as an attempt to limit the application of the doctrine of equivalents to the scope of the claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. All publications cited herein and the materials cited therein are specifically incorporated by reference.

[0205] The singular forms "a," "an," and "the," when used in the specification and the appended claims, 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 the ranges is significant both in relation to the other endpoint and independently of the other endpoint. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that such description includes instances when the event or circumstance occurs and instances when the event or circumstance does not occur.

[0206] Throughout this specification, the word "comprise" and variations of that word, such as "comprising" and "comprises," mean "including, but not limited to," and are not intended to exclude, for example, other additives, components, integers, or steps. The terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific embodiments of the invention, which are also disclosed. "Exemplary" or "for example" means "an example of" and is not intended to convey an indication of a preferred or ideal embodiment. Similarly, "such as" is used in a limiting sense, but rather for descriptive or illustrative purposes.

[0207] Moreover, the invention illustratively disclosed herein may be suitably practiced in the absence of any element not specifically disclosed herein.

Claims

1. an electrode plate including a grid and an active material, the grid including a first grid edge and a second grid edge, the grid having a grid thickness of less than 1.0 mm; a porous membrane disposed adjacent to the electrode plate, the porous membrane having a first side lane adjacent a first membrane edge, a second side lane adjacent a second membrane edge, and a central portion disposed between the first side lane and the second side lane, the first membrane surface having a plurality of primary ribs extending from or into the first membrane surface within the central portion, and a first array of secondary ribs disposed within the first side lane and a second array of secondary ribs disposed within the second side lane; The electrode and separator assembly, wherein the active material covers the entire surface of the grid and is non-uniformly distributed.

2. the first grid edge is located within the first side lane; the grid includes an active material disposed thereon, the active material being non-uniformly disposed on the grid; the grid includes a non-uniform geometric shape; the plurality of primary ribs include a uniform height and a uniform distribution; either or both of the first array of secondary ribs and the second array of secondary ribs are more closely spaced than the plurality of primary ribs; the plurality of primary ribs are longitudinally disposed in a longitudinal direction of the porous membrane; either or both of the first array of secondary ribs and the second array of secondary ribs are not parallel to the plurality of primary ribs; or any of the plurality of primary ribs, the first array of secondary ribs, or the second array of secondary ribs is one of the group consisting of solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs extending longitudinally in a substantially longitudinal direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending transversely in a substantially width direction of the porous membrane, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof; the grid is one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid; The electrode plate is a positive electrode plate, The electrode plate is a negative electrode plate, the grid has a first grid surface and a second grid surface, the active material being more highly distributed on the first grid surface compared to the second grid surface; the porous membrane comprises a second membrane surface having a third array of ribs on the second membrane surface; or 2. The electrode and separator assembly of claim 1, wherein the porous membrane is one of the group consisting of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator.

3. an electrode and separator assembly, the plurality of primary ribs being longitudinally disposed in a machine direction of the porous membrane, either or both of the first array of secondary ribs and the second array of secondary ribs are longitudinally disposed in the longitudinal direction and substantially parallel to the plurality of primary ribs; or 3. The electrode and separator assembly of claim 2, wherein either or both of said first array of secondary ribs and said second array of secondary ribs are laterally disposed in a widthwise direction.

4. either or both of the first array of secondary ribs and the second array of secondary ribs are not parallel to the plurality of primary ribs; and 3. The electrode and separator assembly of claim 2, wherein either or both of said first array of secondary ribs and said second array of secondary ribs are disposed orthogonal to said array of primary ribs.

5. 10. The electrode and separator assembly of claim 1, wherein said porous membrane includes a second membrane surface having a third array of ribs on said second membrane surface.

6. the porous membrane includes a second membrane surface having a third array of ribs on the second membrane surface; 3. The electrode and separator assembly of claim 2, wherein the third array of ribs is one of the group consisting of solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs extending longitudinally in a substantially longitudinal direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending laterally in a substantially width direction of the separator, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof.

7. The porous membrane is one of the group consisting of an envelope, a hybrid envelope, a sleeve separator, a pocket separator, and a wrap separator; 3. The electrode and separator assembly of claim 2, wherein the porous membrane includes at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

8. an electrode plate including a grid having a non-uniform geometry; a porous membrane including a first membrane surface having an array of primary ribs disposed on said first membrane surface and extending from a first membrane edge to a second membrane edge; An electrode and separator assembly comprising: An electrode and separator assembly, wherein said array of primary ribs has a uniform height, and said grid covers an entire surface of said grid and contains active material that is non-uniformly distributed.

9. the grid has a first grid surface and a second grid surface, the active material being more highly distributed on the first grid surface compared to the second grid surface; the grid comprises a thickness of less than 1.0 mm; the grid is one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid; The electrode plate is a positive electrode plate, The electrode plate is a negative electrode plate, said array of primary ribs being longitudinally disposed machine-wise and uniformly laterally spaced widthwise; said array of primary ribs being longitudinally disposed in the machine direction and non-uniformly laterally spaced in the width direction; or the array of primary ribs is one of the group consisting of solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs extending longitudinally in a substantially longitudinal direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending transversely in a substantially width direction of the porous membrane, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof; or The electrode and separator assembly of claim 8 , wherein the first membrane surface faces and is adjacent to the electrode plate.

10. 1. An electrode and separator assembly further comprising a second membrane surface having an array of ribs extending from said second membrane surface, or the array of ribs is one of the group consisting of solid ribs, discrete broken ribs, continuous ribs, discontinuous ribs, discrete peaks, discrete protrusions, angled ribs, angled ribs, linear ribs, ribs extending longitudinally in a substantially longitudinal direction of the porous membrane, ribs extending laterally in a substantially width direction of the porous membrane, ribs extending transversely in a substantially width direction of the porous membrane, discrete teeth, toothed ribs, sawtooth, sawtooth ribs, battlemented, battlemented ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag-sawtooth ribs, broken discontinuous zigzag-sawtooth ribs, grooves, channels, textured regions, embossments, dimples, columns, mini-columns, porous, non-porous, cross ribs, mini-ribs, cross mini-ribs, and combinations thereof; or The electrode and separator assembly of claim 8 , wherein the second membrane surface faces toward and is adjacent to the electrode plate.

11. the porous membrane is one of the group consisting of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator, and optionally The porous membrane is one of the group consisting of an envelope, a hybrid envelope, a sleeve separator, a pocket separator, and a wrap separator; 10. The electrode and separator assembly of claim 8, wherein the porous membrane includes at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

12. An electrode and separator assembly including an electrode plate including a grid and an active material and a porous membrane, the active material covers and is non-uniformly distributed over the entire surface of the grid; the grid includes a first grid edge and a second grid edge; an electrode and separator assembly, wherein the active material is non-uniformly distributed on the grid, and the porous membrane has a support structure supporting the first grid edge and the second grid edge.

13. the first grid edge includes at least a first grid corner and the second grid edge includes at least a second grid corner; or the support structure includes a first array of ribs having a uniform height; the support structure includes a first fiber mat adjacent the first grid edge and a second fiber mat adjacent the second grid edge; the grid has a first grid surface and a second grid surface, the active material being more highly distributed on the first grid surface compared to the second grid surface; the grid is one of the group consisting of a stamped grid, a cast grid, and an expanded metal grid; The electrode plate is a positive electrode plate, or 13. The electrode and separator assembly of claim 12, wherein the electrode plate is a negative plate.

14. an electrode and separator assembly, the support structure including a first array of ribs having a uniform height, the first array of ribs are uniformly spaced laterally from a first membrane edge of the porous membrane to a second membrane edge of the porous membrane; the first array of ribs are non-uniformly spaced laterally from a first membrane edge of the porous membrane to a second membrane edge of the porous membrane; the first array of ribs is more closely spaced in a first membrane region adjacent the first membrane edge and more closely spaced in a second membrane region adjacent the second membrane edge compared to spaced ribs in a central portion of the porous membrane; said first array of ribs being uniformly spaced laterally from a first grid edge to said second grid edge; the first array of ribs are non-uniformly spaced laterally from the first grid edge to the second grid edge; or 14. The electrode and separator assembly of claim 13, wherein the first array of ribs is more densely packed in a first region adjacent the first grid edge and more densely packed in a second region adjacent the second grid edge compared to spaced ribs in a central portion of the grid.

15. 13. The electrode and separator assembly of claim 12, wherein the support structure includes a fiber mat, and optionally the fiber mat extends from the first grid edge to the second grid edge.

16. The porous membrane is one of the group consisting of an envelope separator, a hybrid envelope separator, a sleeve separator, a pocket separator, a wrap separator, a cut piece separator, and a leaf separator, and optionally, the porous membrane is one of the group consisting of an envelope, and a hybrid envelope, a sleeve separator, a pocket separator, and a wrap separator; 13. The electrode and separator assembly of claim 12, wherein the porous membrane includes at least one sealed edge formed by crimping, welding, ultrasonic welding, heat welding, adhesives, and combinations thereof.

17. 13. A lead-acid cell or battery comprising the electrode and separator assembly of claim 1, 8 or 12, optionally comprising: Operates in one of the following states: while driving, while stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial charge state, and combinations thereof; or The lead acid battery is a lead acid cell or battery selected from the group consisting of flat plate batteries, flooded lead acid batteries, reinforced flooded lead acid batteries ("EFB"), valve regulated lead acid ("VRLA") batteries, deep cycle batteries, gel batteries, absorbent glass mat ("AGM") batteries, tubular batteries, inverter batteries, vehicle batteries, starting-lighting-ignition ("SLI") vehicle batteries, idle-start-stop ("ISS") vehicle batteries, car batteries, truck batteries, marine batteries, motorcycle batteries, all terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric car batteries, electric rickshaw batteries, electric three wheeler batteries, and electric bicycle batteries.

18. 20. A system including the lead-acid cell or battery of claim 17, optionally comprising: the system further includes a vehicle, the vehicle being selected from the group consisting of a car, a truck, a motorcycle, an all-terrain vehicle, a forklift, a golf cart, a hybrid vehicle, a hybrid electric vehicle, an electric vehicle, an idle-start-stop ("ISS") vehicle, a water container, an electric rickshaw, an electric three-wheeler, and an electric bicycle; The system is operated in one of the following states: while driving, while stationary, in a backup power application, in a deep cycle application, in a cycle application, in a partial charge state, and combinations thereof; or The system is one of the group consisting of: an uninterruptible power supply, an energy storage system, a power backup system, a renewable energy storage system, and combinations thereof.

19. A stamped plate electrode including a grid and an active material, the active material covering an entire surface of the grid and being non-uniformly distributed, the grid including a first grid edge and a second grid edge, the grid having a grid thickness of less than 1.0 mm; 1. A porous membrane disposed adjacent to an electrode plate, the porous membrane having a first side lane adjacent a first membrane edge, a second side lane adjacent a second membrane edge, and a central portion disposed between the first side lane and the second side lane, the porous membrane including a first membrane surface having a plurality of primary ribs extending from or into the first membrane surface within the central portion, and a first array of secondary ribs disposed within the first side lane and a second array of secondary ribs disposed within the second side lane. an electrode and separator assembly comprising:

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