Battery separator, electrode plate, assembly of battery separator and electrode plate, lead-acid battery and electric vehicle

Abstract

An assembly consisting of an electrode plate and a purely porous membrane separator wherein the electrode plate comprises a grid which is a conductor with openings between the conductors; the grid comprises an active material applied to the grid, and the active material forms granules in the openings; a separator having a first surface facing and directly contacting the negative electrode plate, the first surface having a plurality of columns and / or rows of first ribs, the first ribs having a plurality of discrete protrusions, carbon being coated on the first surface directly contacting the negative electrode plate, and the carbon coating having a thickness of 10 microns; the discrete protrusions prevent the negative electrode active material from falling off and prevent the pellets from being pushed out of the opening. According to the invention, carbon in NAM is removed; and coating a small amount of carbon on the pressure resistant separator, thereby improving the dynamic charge acceptance of the battery.

Description

[0001] This application is a divisional application. The original priority date is September 4, 2018; the original international filing date is September 3, 2019; the original international application number is PCT / US2019 / 049264; the date of entry into the Chinese national phase is April 29, 2021, and the Chinese application number is 201980071915.2; the original invention title is "Battery Separator, Electrode Assembly, System and Related Methods". Technical Field

[0002] The present disclosure is directed to new or improved separators for various lead-acid batteries and / or systems. Additionally, the exemplary embodiments disclosed herein are directed to new or improved battery separators, separator and electrode assemblies including the same, battery cells including the same, batteries including the same, systems including the same, and / or methods of making and / or using the same and / or the like and / or combinations thereof. According to at least selected exemplary embodiments, the present disclosure or invention is at least directed to new or improved battery separators characterized by one or more of the following: anti-plate warping separators, puncture-resistant separators, elastic separators, battery cells, batteries, related methods of using or including the same, related systems of using or including the same, related vehicles of using or including the same, methods of manufacturing the same, and / or the like and / or combinations thereof. According to at least certain exemplary 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 the following: enhanced performance, reduced failure rate, extended service life, reduced occurrence of plate short circuits, reduced occurrence of separator punctures, and / or the like, and / or combinations thereof. Background Art

[0003] Lead-acid batteries have been used in various applications for many years, and thus improving the service life of these batteries has been a goal and will remain important in the foreseeable future. The goal is to increase the battery life while at least maintaining or even increasing the battery capacity. The positive electrode plate is typically made of lead dioxide (PbO doped with positive electrode active material (PAM)) 2)(or its alloy) grid structure. The negative electrode plate is usually constructed of lead (Pb) (or its alloy) doped with negative electrode active material (NAM) and having a grid structure. The grid usually has a grid structure of conductors and has openings between the conductors. Since the active material is applied on the grid, agglomerates are formed in the openings. For lead-acid batteries, shedding of the active material has always been a problem, but it seems to be exacerbated with the emergence of serrated and stacked ribs (such as those disclosed in U.S. Patent No. 7,094,498, the content of which is incorporated herein). The serrated or stacked ribs may press on the agglomerates and push the agglomerates into and out of the openings, thus offsetting the efficacy of the active material. This is especially a problem when the openings or gaps between the serrations or stacks are located on the conductors such that the serrations or stacks extend further into the openings.

[0004] So far, as far as the inventors know, there is no means to solve the above problems by using battery separators.

[0005] For at least certain applications or batteries, such as the above exemplary cases, there is still a need for improved separators to provide reduced battery failures, increased battery cycle life, and / or improved performance in a partial state of charge and / or the like. More particularly, there is still a need for improved separators, improved batteries, and improved systems, such as those having the following: separators with increased durability, reduced occurrence of shedding and piercing of the active material, batteries with reduced short-circuit conditions, reduced water loss in the battery, lower battery floating current, improved battery operation in a partial state of charge, extended battery life, reduced battery failures, improved batteries using improved separators, improved systems using improved batteries (which use improved separators), and / or the like. More particularly, there is still a need for improved separators, improved batteries, and improved systems, such as those that work with warped plates or plates prone to warping using improved separators, which provide extended battery life and / or reduced battery failures in lead-acid batteries. Summary of the Invention

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

[0007] According to at least selected exemplary embodiments, aspects or objectives, the present disclosure or invention can solve at least the above difficulties, problems or requirements, and / or can provide a new or improved separator, a warpage-resistant separator and / or a lead-acid battery separator, a new or improved battery cell or battery using the new or improved separator, and / or a new or improved system using the new or improved separator, battery cell or battery. According to at least specific 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 manufacturing and / or using such new or improved battery separators, battery cells, batteries, and / or systems.

[0008] According to at least specific exemplary embodiments, aspects or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery, which has at least an improved formulation and rib configuration to reduce or mitigate the warping of electrode plates and / or the effects of electrode plate warping, reduce the occurrence of separator piercing, reduce the occurrence of battery electrode short circuits, and / or the like and / or combinations thereof. According to at least specific exemplary embodiments, aspects or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery, which may be characterized by at least one or more of the following: anti-plate warping, puncture resistance, oxidation resistance, acid mixing, reduced resistance, improved wettability, improved fillers, optimized porosity, optimized tortuosity, reduced thickness, reduced backsheet thickness, with ribs, negative side cross ribs (NCR), reduced oil content, increased acid diffusion, enhanced oxidation resistance or improved oxidation stability, optimized porosity, optimized pore tortuosity, improved acid diffusion, and / or the like, and / or combinations thereof. According to at least specific exemplary embodiments, aspects or objectives, the present disclosure or invention is directed to an improved separator for a lead-acid battery, which can provide at least one or more of the following: low water loss in the battery and / or battery cell, reduced resistance in the battery and / or battery cell, increased acid mixing in the battery and / or battery cell, reduced acid stratification in the battery and / or battery cell, improved performance in the battery and / or battery cell, extended service life in the battery and / or battery cell, reduced failure rate in the battery and / or battery cell, and / or the like; and / or combinations thereof.

[0009] According to at least certain exemplary embodiments, aspects, or purposes, the present disclosure or invention is directed to separators, and / or improved battery cells and / or batteries using improved separators, and / or improved systems using improved battery cells and / or batteries (which use improved separators), which at least overcome the foregoing difficulties and / or problems. 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 the following: enhanced performance, reduced failure rate, extended service life, reduced occurrence of plate short circuits, reduced occurrence of separator punctures, reduced water loss, reduced floating charge current, improved charging termination current, improved charging acceptability, improved energy throughput, reduced antimony (Sb) poisoning, reduced acid stratification, reduced acid starvation, reduced dendrite formation, reduced internal resistance, improved cold cranking amperage (CCA), improved uniformity, improved cycling performance, and / or the like, and / or combinations thereof.

[0010] According to at least selected exemplary embodiments, aspects, or purposes, the present disclosure or invention is at least directed to new or improved battery separators, anti-warping separators, puncture-resistant separators, resilient separators, battery cells, batteries, methods involving them, systems using them, vehicles using them, methods of manufacturing them, methods of using them, and combinations thereof.

[0011] According to at least certain exemplary embodiments, aspects, or purposes, the present disclosure or invention is directed to new or improved battery separators for use in various batteries and / or applications. An exemplary list of such batteries and / or applications includes: flat plate batteries, tubular batteries, flooded lead acid batteries, enhanced flooded lead acid (EFB) batteries, valve-regulated lead acid (VRLA) batteries, deep cycle batteries, gel batteries, absorbed glass mat (AGM) batteries, inverter batteries, power harvesting batteries, power storage batteries, batteries for internal combustion engines, auxiliary batteries, starting lighting ignition (SLI) batteries, idle start-stop (ISS) batteries, vehicle batteries, passenger vehicle batteries, automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, marine batteries, aircraft batteries, forklift truck batteries, golf cart or golf car batteries, hybrid electric vehicle (HEV) batteries, mild 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 a partial state of charge (PSoC), and / or the like, and combinations thereof.

[0012] According to at least selected exemplary embodiments, aspects, or purposes, an overcharge system with a battery of the present invention is provided, the battery incorporating a separator of the invention as described herein. Exemplary systems can be one or more of the following: a vehicle, a UPS, an auxiliary power system, a power collector system, a renewable energy collector system, a wind power collector system, a solar power collector system, a backup power system, an inverter, and combinations thereof. Further, exemplary vehicles can be one of the following: an automobile, a passenger vehicle, a truck, a forklift, a hybrid vehicle, an HEV, a micro hybrid vehicle, an ISS vehicle, an electric vehicle, a ship, an airplane, an electric rickshaw, an electric tricycle, an electric bicycle, a motorcycle, an all-terrain vehicle, a golf cart or golf car and / or the like, and combinations thereof.

[0013] In a first exemplary embodiment of the present disclosure or invention, an electrode and separator assembly is provided with an electrode plate having a grid and active material thereon. The grid has at least one grid edge. Further, the active material is unevenly distributed on the grid. A porous membrane is arranged adjacent to the electrode plate with a first membrane surface. The first membrane surface has a first surface edge and a second surface edge and a plurality of ribs extending from the surface of the membrane; the plurality of ribs extend from the first surface edge to the second surface edge.

[0014] In another exemplary embodiment of the present invention or disclosure, an electrode and separator assembly is provided with an electrode plate, which can be a positive electrode or a negative electrode, having a grid and active material unevenly distributed thereon. The grid has a first grid edge and a second grid edge. A porous membrane is arranged adjacent to the electrode plate. The porous membrane has a first side channel adjacent to the first membrane edge and a second side channel adjacent to the second membrane edge, and a central portion between the first side channel and the second side channel. The porous membrane has a first membrane surface having a plurality of main ribs extending out of or into the first membrane surface within the central portion, and a first set of secondary ribs arranged in the first side channel and a second set of secondary ribs arranged in the second side channel.

[0015] In one aspect of the present invention, the first grid edge can be arranged in the first side channel and the second grid edge can be arranged in the second side channel. The plurality of main ribs can have a uniform height and a uniform distribution. And either or both of the first set of secondary ribs and the second set of secondary ribs are spaced more closely than the plurality of main ribs. The plurality of main ribs, the first set of secondary ribs, and / or the second set of secondary ribs can be arranged longitudinally and substantially parallel to the processing direction of the porous membrane, or arranged transversely and substantially parallel to the cross-processing direction of the porous membrane. Either or both of the first set of secondary ribs and the second set of secondary ribs can be substantially parallel, orthogonal, or angled with respect to the plurality of main ribs. The porous membrane can have a second membrane surface having a third set of ribs thereon.

[0016] In another aspect of the present invention, the grid can be any one of a stamped grid, a cast grid, or an expanded metal grid. Further, the grid may undergo warping. The grid can have a first grid surface and a second grid surface, and wherein, compared with the second grid surface, the active material can be more heavily distributed on the first grid surface. Further, the active material can be unevenly distributed on the grid surface.

[0017] In yet another aspect, the plurality of main ribs, the first set of secondary ribs, the second set of secondary ribs, and / or the third set of ribs can be one or more of the following: uninterrupted ribs, discretely discontinuous ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, diagonal ribs, linear ribs, ribs extending substantially longitudinally in the processing direction of the porous membrane, ribs extending substantially transversely across the processing direction of the porous membrane, ribs extending transversely across the processing direction of the separator, discrete teeth, toothed ribs, serrated protrusions, serrated ribs, stack-like protrusions, stack-like ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag serrated ribs, discontinuous zigzag serrated ribs, grooves, trenches, textured areas, protrusions, depressions, columns, micro-columns, porous, non-porous, cross ribs, micro-ribs, cross micro-ribs, negative cross ribs (NCR), and combinations thereof.

[0018] In a specific embodiment, the porous membrane can be one of the following: an envelope, a hybrid envelope, a sleeve separator, a bag separator, a sheet, a leaf, a serpentine, a fold, a plate wrap, and / or a wrapped separator (with or without non-woven fabric, such as a glass mat or sticker paper, on one or both sides). The porous membrane can have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof. The porous membrane can also be a slice.

[0019] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly is provided with an electrode plate, which can be a positive electrode or a negative electrode, having a grid and an active material non-uniformly distributed thereon. The porous membrane can be provided with a first membrane surface having an array of main ribs located thereon and extending from a first membrane edge to a second membrane edge; wherein, the array of main ribs has a uniform height.

[0020] Another aspect of the present invention or disclosure provides a grid having a first grid surface and a second grid surface, on which the active material is more heavily distributed compared with the second grid surface. As an alternative, or additionally, the active material can be unevenly distributed on the surface of the grid. The grid can be one of the following: a stamped grid, a cast grid, and an expanded metal grid. Additionally, the grid may undergo warping. Either the first membrane surface or the second membrane surface can be adjacent to the electrode plate.

[0021] In another aspect of the present invention or disclosure, the main rib array can be arranged longitudinally and substantially parallel to the processing direction of the porous membrane, and can be laterally spaced evenly or unevenly across the entire processing direction of the porous membrane. The porous membrane is provided with a second surface, and a second set of ribs can extend from the second surface.

[0022] In another aspect of the present invention or disclosure, one or both of the main rib array and / or the second set of ribs can be one or more of the following: uninterrupted ribs, discretely discontinuous ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, diagonal ribs, linear ribs, ribs extending substantially longitudinally in the processing direction of the porous membrane, ribs extending substantially laterally across the processing direction of the porous membrane, ribs extending transversely across the processing direction of the separator, discrete teeth, toothed ribs, serrated protrusions, serrated ribs, battlemented protrusions, battlemented ribs, battlemented serrated ribs, battlemented Rip Tide ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag serrated ribs, discontinuous zigzag serrated ribs, grooves, channels, textured areas, protrusions, depressions, columns, micro-columns, porous, non-porous, cross ribs, micro-ribs, cross micro-ribs, negative cross micro-ribs, and combinations thereof.

[0023] In an exemplary aspect, the porous membrane can be one of the following: an envelope separator, a hybrid envelope separator, a sleeve separator, a bag separator, a wrapped separator, a sliced separator, a blade separator; wherein, the envelope, hybrid envelope, sleeve separator, bag separator, and wrapped separator can have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof.

[0024] In yet another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly can be provided with an electrode plate provided with a grid and active material. The grid can have a first grid edge and a second grid edge, and the active material can be unevenly distributed on the grid. The porous membrane can be further provided with a first membrane surface having a support structure for supporting the first grid edge and the second grid edge. The first grid edge can have at least a first grid corner, and the second grid edge can have at least a second grid corner. The support structure can have a first set of ribs having a uniform height.

[0025] The grid can have a first grid surface and a second grid surface, wherein, compared with the second grid surface, the active material can be more heavily distributed on the first grid surface. As an alternative, or additionally, the active material can be unevenly distributed on the surface of the grid. The grid can be one of the following: a stamped grid, a cast grid, and an expanded metal grid. The electrode plate may be subject to warping.

[0026] In certain exemplary aspects, the first set of ribs may be evenly laterally spaced from a first membrane edge of the porous membrane to a second membrane edge of the porous membrane. The first set of ribs may also be evenly or unevenly laterally spaced from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane.

[0027] In other exemplary aspects of the present disclosure, compared to the rib spacing in the central portion of the porous membrane, the first set of ribs may be more closely spaced in a first membrane region adjacent to the first membrane edge and more closely spaced in a second membrane region adjacent to the second membrane edge.

[0028] In yet another exemplary aspect of the present disclosure, the first set of ribs may be evenly or unevenly laterally spaced from a first grid edge to a second grid edge. Additionally, compared to the rib spacing in the central portion of the grid, the first set of ribs may be more closely spaced in a first region adjacent to the first grid edge and more closely spaced in a second region adjacent to the second grid edge.

[0029] In yet another aspect of the present disclosure, the support structure may have a fibrous mat that extends from the first grid edge to the second grid edge. The support structure may have a first fibrous mat adjacent to the first grid edge and a second fibrous mat adjacent to the second grid edge.

[0030] In another exemplary aspect, the porous membrane may be one of the following: an envelope separator, a hybrid envelope separator, a sleeve separator, a bag separator, a wrap separator, a slice separator, and a vane separator; wherein, the envelope, hybrid envelope, sleeve separator, bag separator, and wrap separator may have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof.

[0031] In yet another exemplary embodiment of the present disclosure, a lead-acid battery may be provided with a separator as fully described herein. The lead-acid battery may operate in one of the following states: in motion, at rest, in a standby power application, in a deep cycle application, in a cycling application, in a partially charged state, and combinations thereof.

[0032] Exemplary batteries may be one of the following: flat batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, 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, automotive batteries, truck batteries, marine batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric tricycle batteries, and electric bicycle batteries.

[0033] In yet another exemplary embodiment, the system may be provided with a lead acid battery as described herein. The system may be provided with a vehicle, where the vehicle may be one of the following: 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 marine vessel, an e-rickshaw, an e-rickshaw, and an electric bicycle. Further, the system may operate in one of the following states: in motion, stationary, in a standby power application, in a deep cycle application, in a cycling application, in a partially charged 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.

[0034] In yet another exemplary embodiment, a method for reducing grid warping in an electrode and separator assembly may be provided. The method may provide an electrode plate having a grid prone to warping; a porous membrane adjacent to the grid; a support structure placed between the porous membrane and the grid. The active material may be applied unevenly to the grid. The grid may have an outer edge. The support structure may overlap at least a portion of the outer edge of the grid. The support structure may be provided as a set of ribs extending from the porous membrane having a uniform height. The set of ribs may be arranged longitudinally along the processing direction of the porous membrane, and the set of ribs may be evenly spaced in a transverse dimension from a first edge of the outer edge to a second edge of the outer edge across the processing direction. As an alternative, or additionally, the support structure may have or be a polygonal spacer. As an alternative, or additionally, the support structure may have or be a fibrous mat. As an alternative, or additionally, the support structure may have or be a first fibrous mat and a second fibrous mat, where the first fibrous mat is provided to at least partially overlap the first edge of the outer edge and the second fibrous mat is provided to at least partially overlap the second edge of the outer edge. The method may further provide subjecting the electrode and separator assembly to high temperature and / or thermal cycling.

[0035] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention provides a separator, its components, and physical properties and characteristics that are synergistically combined in an unexpected manner to address previously unmet needs in the lead acid battery industry with an improved battery separator. In a particular preferred exemplary embodiment, the present disclosure or invention provides a battery using a separator as described herein to address previously unmet needs in the lead acid battery industry with an improved lead acid battery separator in an unexpected manner. In a particular preferred exemplary embodiment, the present disclosure or invention provides a system using a battery as described herein to address previously unmet needs in the lead acid battery industry with an improved system (which uses the lead acid battery of the present invention, which uses the separator of the present invention as described herein) in an unexpected manner.

[0036] According to at least selected exemplary embodiments, aspects or objectives, the present invention solves, meets and / or overcomes at least in part the difficulties, requirements and / or problems which have not hitherto been solved, met and / or addressed by the current state of the art. According to at least a particular objective, the present invention provides an improved separator, an improved battery using the improved separator and / or an improved system using the improved battery, which overcomes at least the aforementioned difficulties. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is a schematic illustration of a typical lead-acid battery.

[0038] Figure 2A depicts a rib pattern longitudinally arranged on a separator in the machine direction md.

[0039] Figure 2B depicts a rib pattern transversely arranged on a separator in the cross machine direction cmd.

[0040] Figure 3A and Figure 3B show exemplary lead-acid battery plates.

[0041] Figures 4A to 4D illustrates lead-acid battery plates with different types of coated active materials.

[0042] Figure 5A is a plan view of a warped plate. Figure 5B is Figure 5A a side view of the warped plate of Figure 5C shows adjacent electrode plates and separator assemblies having warped plates and the pinch points they generate.

[0043] Figure 6A and Figure 6B show various exemplary separators and rib configurations for resisting plate warping.

[0044] Figures 7A to 7C shows various exemplary electrode plates and separator assemblies having the exemplary inventive separator of the present invention. Figure 7A shows as Figure 2A and Figure 2B generally shown in Figure 7B shows as Figure 6A generally shown in Figure 7C shows as Figure 6B generally shown in

[0045] Figure 8A and Figure 8B show a conventional separator deflected by swelling with active material.

[0046] Figure 8C and 8D shows the separator of the present invention that resists the expansion of the active material.

[0047] Figure 9A and 9B depicts the rib configuration of an exemplary separator of the present invention.

[0048] Figure 10A and 10B shows the electrode surface and part, which are supported by the separator of the present invention.

[0049] Figure 11 is a graph and table describing the brittleness of silica of the present invention.

[0050] Figures 12A to 12C shows a sample and test fixture for testing the antioxidant properties of a material.

[0051] Figure 13 shows a puncture tip.

[0052] Figure 14 shows the battery life illustration of SLI, EFB, and AGM batteries under partial state of charge (PSoC) cycling tests.

[0053] Figure 15 shows conventional battery overcharge, where acid stratification is prevented by the evolution of oxygen and hydrogen.

[0054] Figure 16 depicts the mixing of batteries with complete acid stratification, which have a conventional uninterrupted rib SLI separator, a serrated rib separator, and an optimized ribbed separator according to some exemplary embodiments described herein.

[0055] Figure 17 shows a battery test motion platform to simulate the gravity experienced by a vehicle.

[0056] Figure 18 shows the comparative performance data of a computer-optimized hybrid separator (Rip Tide M) with Figure 16 the separator with an uninterrupted rib configuration in

[0057] Figure 19 shows the effect of the expansion of the active material as the number of separator ribs increases.

[0058] Figure 20 shows the acid mixing effect of the increase in the number of ribs on the separator.

[0059] Figure 21 shows the PSoC cycling test of a ribbed separator according to some exemplary embodiments described herein.

[0060] Figure 22 Shows the failure of a conventional SLI separator when operating under PSoC.

[0061] Figure 23 Shows the PSoC cycling effect in a battery having a compression-resistant separator according to some embodiments described herein.

[0062] Figure 24 Shows the PSoC cycling effect in a battery having a compression-resistant separator according to some embodiments described herein.

[0063] Figure 25 Shows the growth formation of lead sulfate crystals on the electrode surface.

[0064] Figure 26 Shows a schematic comparison of a carbon-containing active material and a carbon-coated compression-resistant separator according to some embodiments described herein.

[0065] Figure 27 Shows a carbon-coated compression-resistant separator according to some embodiments described herein.

[0066] Figure 28 Shows the effect of a nucleating additive coating on a compression-resistant separator according to some embodiments described herein.

[0067] Throughout the drawings (illustrations), the same or corresponding elements or parts are denoted by the same reference numerals. Further, unless otherwise specified, no drawing should be construed as being drawn to scale. Dimensions shown in the various figures are in millimeters. Detailed Description

[0068] According to at least selected exemplary embodiments, objects, or aspects, the present disclosure or invention addresses and in some cases exceeds the foregoing problems or needs. According to at least certain exemplary embodiments, objects, or aspects, the present disclosure or invention may provide an improved separator and a battery cell and / or battery using the same, and / or a related system using the same, and / or a related method using the same. According to at least selected exemplary embodiments, aspects, or objects, the present disclosure or invention is at least directed to a new or improved battery separator characterized by one or more of the following: an anti-plate warping separator, a puncture-resistant separator, an elastic separator, a battery cell, a battery, a related method using or involving the same, a related system using or involving the same, a related vehicle using or involving the same, a method of manufacturing the same, and / or the like and / or combinations thereof. According to at least selected exemplary embodiments, aspects, or objects, 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 the following: enhanced performance, reduced failure rate, extended service life, reduced occurrence of plate short circuits, reduced occurrence of separator punctures, and / or the like, and / or combinations thereof.

[0069] Now referring Figure 1 , an exemplary lead-acid battery 100 has an array 102 that is an alternating array of positive plates 200 (or positive electrodes) and negative plates 201 (or negative electrodes), with separators 300 interposed between the respective electrodes 200, 201. The array 102 is substantially immersed in an electrolyte 104. The electrolyte 104 can be, for example, a solution of sulfuric acid (H 2 SO 4 ) and water (H 2 O). The electrolyte solution can have a specific gravity in the range of about 1.215 to about 1.300, for example, about 1.28. The battery 100 is further provided with 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.

[0070] Referring Figure 2A and Figure 2B , an exemplary separator 300 can be provided with a porous membrane backing web 302 having sets of ribs 304, 305 extending therefrom. As Figure 2A shown, an exemplary first set of ribs 304 are longitudinally arranged in the machine direction md of the separator 300. As Figure 2B shown, an exemplary second set of ribs 305 are transversely arranged in the cross machine direction cmd of the separator 300 and are thus referred to as cross ribs. When placed in a battery, the exemplary separator 300 can be placed such that the first set of ribs 304 are adjacent to the positive plate 200 and are referred to as positive ribs 304, while the second set of ribs 305 are adjacent to the negative plate 201 and are referred to as negative ribs, or vice versa. As Figure 2BAs shown, since it extends across the processing direction cmd, the second set of ribs can be referred to as cross ribs (e.g., "negative cross ribs" if they face the negative electrode plate 201). Further, when placed in the battery 100, either of the rib sets 304, 305 can face either of the electrode plates 200, 201.

[0071] Any one of the rib sets 304, 305 can be configured with an excessive structure, shape, configuration, or pattern, which can be a uniform group, an alternating group, or a mixture or combination of the following: uninterrupted ribs, discrete interrupted ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, diagonal ribs, linear ribs, ribs that extend longitudinally substantially in the processing direction md of the separator (i.e., from the top to the bottom of the separator 300 in the battery), ribs that extend transversely substantially in the cross-processing direction cmd of the separator (i.e., in the transverse direction of the separator 300 in the battery, perpendicular to the processing direction md), ribs that extend crosswise substantially in the cross-processing direction cmd of the separator 300, discrete teeth, toothed ribs, serrated protrusions, serrated ribs, stack-like protrusions, stack-like ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag serrated ribs, discontinuous discontinuous zigzag serrated ribs, grooves, trenches, textured areas, protrusions, depressions, columns, micro-columns, porous, non-porous, cross ribs, micro-ribs, cross micro-ribs, and combinations thereof. The ribs 304, 305 are further described herein.

[0072] Plate structure

[0073] Referring Figures 2A to 4D , the electrode plates 200, 201 are made of at least the grid 202 and the active material 203. The grid 202 can be manufactured in different ways, such as by casting metal, expanded metal, and stamped metal. Additionally, different grids within the battery can be manufactured using different methods from each other. For example, the positive grid can be stamped metal, while the negative grid can be expanded metal. As mentioned above, the stamped grid uses less lead than other methods and is thus more cost-effective. Although the stamped grid reduces costs, thinner plates have a greater tendency to warp, deform, bend, twist, bow, and / or cupping. This leads to the possibility of pinch points, wear points, or puncture points. When one or more plates cut or puncture the separator, it is very likely to contact the adjacent plate and short-circuit the battery and / or the battery cell.

[0074] As used herein, throughout the specification and claims, the term "warp" and its variants, in addition to having its general and customary meaning, can also be used interchangeably with at least the following terms and their variants: deform, bend, twist, bow, and / or cup, and these words should also have their general and customary meanings.

[0075] Continuing reference Figures 2A to 4D , the grid 202 is typically doped or pasted with an active material 203. The positive electrode plate 200 is typically doped with a positive active material (PAM), while the negative electrode plate 201 is typically doped with a negative active material (NAM). The active material 203 enhances the function of the grid.

[0076] Now referring to Figure 3A and 3B , a typical grid 202 is provided with a main grid portion 202a and a connector 202b for the lead bars within the battery. An exemplary typical main grid portion 202a has a first vertical side 204a, a second vertical side 204b, a bottom horizontal edge 204c, and a top horizontal edge 204d. The typical main grid portion 202a is further provided with four corners 206a, 206b, 206c, 206d, which may or may not be rounded. The main grid portion 202a is further provided with a lattice structure, which creates a series of openings throughout the grid 208. This helps to reduce weight and material and better utilize the entire grid during the electrochemical reaction of the battery.

[0077] Now referring to Figures 4A to 4D , which shows the plates 200, 201 with the grid 202, having the active material 203 deposited thereon imperfectly with different uniformities. Figures 4A to 4D Exemplary plates 200, 201 are shown with the active material imperfectly distributed across the face of the grid. The darker regions may represent a heavier coating of the active material compared to the lighter regions. Figure 4A Depicts a symmetric distribution of the active material. Figure 4B Illustrates an asymmetric distribution of the active material. Figure 4C Shows a bimodal symmetric distribution of the active material. Figure 4D Depicts an exemplary manner in which the plates 200, 201 may warp as indicated by the arrows. It should be understood that the warped plates 200, 201 may warp, bend, or curve along or around any axis relative to the grid 202. It should also be understood that the warped plates 200, 201 may warp, bend, or curve along or around multiple axes relative to the grid 202. The active material 203 may also be substantially uniformly distributed on the grid 202 (such an embodiment is not shown). Similarly, it may be a slightly non-uniform distribution, with more active material 203 on the right side of the grid 202 relative to the left side (such an embodiment is not shown). Finally, it may be a more severe non-uniform distribution, with more active material 203 on the right side of the grid 202 relative to the left side (such an embodiment is not shown).

[0078] For example, Figure 5A and Figure 5BDepicts exemplary warped electrode plates 200, 201. This particular plate 200, 201 is shown warping about a single axis 210, but multi-axis warping can also occur. Figure 5C Is a top-down cross-sectional view of an array 102 of separator / electrode assemblies 400. The array is shown having two positive electrode plates 200, two negative electrode plates 201, and a typical commercially known separator 300 that encapsulates the positive electrode plate 200 (which is not designed to accommodate warped plates). Since the plates 200, 201 warp and are not flat as expected, they form pinch points 402, which may cut or wear through the separator 300 of the plates 200, 201, causing the plates to contact each other and short-circuiting the battery cells and / or batteries in which they are placed.

[0079] The inventors have further noted that conditions of high grid corrosion and cycling in a partial state of charge also tend to exacerbate plate warping. Accordingly, measures for exemplary separators are provided herein to help mitigate grid corrosion. It is believed that an imperfect distribution of active material on the grid causes uneven expansion and contraction of the plates during cycling, resulting in plate warping.

[0080] Separator description

[0081] Exemplary separators may be provided with a porous membrane network, such as a microporous membrane, mesoporous membrane having pores less than about 5 μm, preferably less than about 1 μm, or a macroporous membrane having pores greater than about 1 μm. The porous membrane may preferably have a pore size from sub-micron up to 100 μm, between about 0.1 μm to about 10 μm in certain embodiments. In certain embodiments, the porosity of the separator membranes described herein may be greater than 50% to 60%. In certain selected embodiments, the porous membrane may be flat or have ribs extending from its surface.

[0082] Exemplary separator 300 may be provided as a flat plate, one or more blades, wrappings, sleeves, or provided as an envelope or bag-like separator. Exemplary envelope separators may preferably have a folded, wrinkled, sealed, and / or the like bottom edge 301c, and the side edges 301a, 301b may be continuous or discontinuous sealed edges. Each edge may be bonded or sealed by adhesion, heating, ultrasonic welding, and / or the like or a combination thereof. Exemplary envelope separators may encapsulate the positive electrode (i.e., positive electrode encapsulating separator), which causes the separator to have two inner sides facing the positive electrode and two outer sides facing the adjacent negative electrode. As an alternative, another exemplary envelope separator may encapsulate the negative electrode (i.e., negative electrode encapsulating separator), which causes the separator to have two inner sides facing the negative electrode and two outer sides facing the adjacent positive electrode. In certain exemplary embodiments, the battery may employ one or both of a positive electrode encapsulating separator and a negative electrode encapsulating separator.

[0083] Certain exemplary separators can be processed to form a hybrid envelope. The hybrid envelope can be provided by forming one or more slits or openings before, during, or after folding the separator sheet in half and / or before, during, or after bonding or sealing the edges of the separator sheet together to form an envelope. The slit or opening can be provided within any closed edge of the separator, such as a sealed edge, but is preferably provided within the bottom crease. The top of the separator is typically open. The length of the opening can be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the length of the entire closed edge. The length of the opening can be from 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the length of the entire closed edge. The hybrid envelope can have 1 - 5, 1 - 4, 2 - 4, 2 - 3, or 2 openings, which may or may not be evenly spaced along the length of the sealed edge. Preferably, there are no openings at the envelope corners.

[0084] Rib

[0085] As described above, the exemplary separator 300 can have a first set of ribs 304 adjacent to the positive electrode plate 200, while a second set of ribs 305 is adjacent to the negative electrode plate 201, or vice versa. Further, either of the sets 304, 305 can take various forms.

[0086] For example, any one or both of the rib arrays 304, 305 can be a uniform group, an alternating group, or a mixture or combination of the following: uninterrupted ribs, discrete interrupted ribs, continuous ribs, discontinuous ribs, discontinuous peaks, discontinuous protrusions, angled ribs, diagonal ribs, linear ribs, ribs extending substantially longitudinally in the machine direction md of the separator [i.e., from the top to the bottom of the separator 300 in the battery 100 (see Figure 2A )], ribs extending substantially transversely in the cross - machine direction cmd of the separator (i.e., in the transverse direction of the separator 300 in the battery 100 (see Figure 2B ), orthogonal to the machine direction md), ribs extending substantially cross - cutting in the cross - machine direction of the separator, discrete teeth, toothed ribs, serrated protrusions, serrated ribs, stack - like protrusions, stack - like ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S - shaped ribs, continuous zigzag serrated ribs, discontinuous zigzag serrated ribs, grooves, channels, textured areas, protrusions, depressions, pillars, micro - pillars, porous, non - porous, cross - ribs, micro - ribs, cross - micro - ribs, and any combination thereof.

[0087] Further, ribs 304, 305 can be a plurality of ribs defined by an angle that is neither parallel nor orthogonal to the edge of the separator, preferably discontinuous ribs. In other words, the angle can be defined as being between greater than zero degrees (0°) and less than 180 degrees (180°) or greater than 180 degrees (180°) and less than 360 degrees (360°) relative to the processing direction of the separator. Additionally, the angle can be defined as being between greater than zero degrees (0°) and less than 180 degrees (180°) or greater than 180 degrees (180°) and less than 360 degrees (360°) relative to the cross-processing direction of the separator. The angled rib pattern can be preferably possible. RipTide TM An acid mixing rib configuration that can help mitigate, reduce, or eliminate acid stratification in a particular battery. When an exemplary battery is in motion, preferably during start-stop motion, and when the porous membrane 302 is substantially aligned and parallel with the motion vector, the selected mixing rib configuration tends to exhibit optimal efficacy.

[0088] In a particular exemplary embodiment, when disposed within an exemplary battery Figure 2A rib 304 can face the positive electrode plate and is thus referred to as the positive rib 304. And when disposed within an exemplary battery Figure 2B rib 305 can face the negative electrode plate and is thus referred to as the negative rib 305.

[0089] In a selected exemplary embodiment, at least a portion of the negative rib can preferably have a height that is about 5% to about 100% or even greater than 100% of the height of the positive rib. In some exemplary embodiments, the height of the negative rib can be at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95%, or 100% compared to the height of the positive rib. In other exemplary embodiments, the height of the negative rib can be no greater than about 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5% compared to the height of the positive rib.

[0090] In some selected embodiments, at least a portion of the porous membrane may have negative electrodes ribs that are longitudinal, transverse, or cross ribs. The negative electrodes ribs may be parallel to the cross machine direction cmd of the separator, or may be set at an angle thereto. For example, the negative electrodes ribs may be oriented at about 0°, 5°, 15°, 25°, 30°, 45°, 60°, 70°, 80°, or 90° relative to the cross machine direction cmd. The cross ribs may be oriented at about 0° to about 30°, about 30° to about 45°, about 45° to about 60°, about 30° to about 60°, about 30° to about 90°, or about 60° to about 90° relative to the cross machine direction cmd.

[0091] As Figure 2A and Figure 2B shown, either of the arrays 304, 305 may extend uniformly from the first side 301a to the second side 301b across the entire width of the separator 300. This is referred to as a general configuration.

[0092] As an alternative and with reference to Figure 6A and Figure 6B , an exemplary separator of the present disclosure may have a central portion 306a and side channels 306b adjacent to the transverse perpendicular sides 301a, 301b, with ribs 304b distributed therein or none at all, in which case the side channels 306b will be flat. The ribs 304a in the central portion 306a may be referred to as main ribs, and the ribs 304b in the side channels 306b may be referred to as secondary ribs. These secondary ribs 304b may be spaced more closely, smaller, larger than the main ribs 304a, or a combination thereof. For example, the secondary ribs 304b may be about 25% to about 100% or greater than about 100% of the height of the main ribs 304a, spaced more closely than the spacing of the main ribs 304a, or a combination thereof. As Figure 6A and 6B further shown in Figure 6A and Figure 6B , exemplary secondary ribs 304b may be distributed longitudinally and aligned with the machine direction md ( Figure 6A ), or distributed transversely and aligned with the cross machine direction cmd ( Figure 6B ). Although not shown, exemplary secondary ribs 304b may be distributed at an angle relative to the machine direction md and the cross machine direction cmd. The exemplary secondary ribs 304b may be uniformly distributed at the same angle, or the angles may also vary among the secondary ribs 304b to possibly create a pattern.

[0093] As Figure 6A and Figure 6BFurther shown, the outlines of electrode plates 200, 201 are shown in dashed lines to superimpose their positions on the separator 300. As can be seen, the corners 206a, 206b, 206c, 206d of the plates are preferably contained or at least partially contained within the side channel 306b. Thus, when the plate-separator assembly 400 is placed in the battery and under pressure, the secondary ribs 304b help to keep the corners 206a, 206b, 206c, 206d parallel. Additionally, the vertical plate edges 204a, 204b are also preferably contained or at least partially contained within the side channel 306b. Thus, when the plate-separator assembly 400 is placed in the battery and under pressure, the secondary ribs 304b help to keep the vertical plate edges 204a, 204b parallel.

[0094] The side channel 306b can further help to seal one edge of the exemplary separator 300 to another edge of the separator 300, as done when encapsulating the separator 300, which will be discussed herein. For example, the seal line 308 (shown as a superimposed dashed line) can pass through at least a portion of the side channel 306b.

[0095] Now referring to Figures 7A - 7C , which depicts an exemplary electrode plate and separator assembly 400 of the present invention with a different separator 300. As shown, the positive electrode plate 200 is encapsulated such that the positive ribs 304, 304a, 304b are adjacent to the plate 200. Although not the configuration shown, it should be understood that the plate 200 can be a negative electrode plate.

[0096] Referring to Figure 7A , the exemplary plate and separator assembly 400 is provided with a separator 300 having a general configuration. The rib 304 can coincide with the side edge of the plate 200. Referring to Figure 7B , the exemplary plate and separator assembly 400 is provided with a separator having main ribs 304a and secondary ribs 304b. The secondary ribs 304b are shown as being distributed substantially parallel to the processing direction and substantially orthogonal to the cross-processing direction cmd. The side edges of the plate 200 are preferably contained or at least partially contained within the side channel 306b. Referring to Figure 7C , the exemplary plate and separator assembly 400 is provided with a separator having main ribs 304a and secondary ribs 304b. The secondary ribs 304b are shown as being distributed substantially parallel to the cross-processing direction cmd and substantially orthogonal to the processing direction. The side edges of the plate 200 are preferably contained or at least partially contained within the side channel 306b.

[0097] As Figures 7A - 7C pointed out, the separator 300 can be formed into an envelope as generally described herein by sealing the separator edges at the lines designated as "joints".

[0098] Specific objectives of the present invention include minimizing the effects of swelling of the negative active material (NAM), which tends to lead to acid starvation, while also maximizing acid mixing using any movement the battery may undergo to reduce the effects of acid stratification. Both of these are problems exhibited by batteries operating in a partial state of charge. For example, Figure 14 Compare the battery life of a conventional SLI battery, an EFB battery, and an AGM battery when undergoing PSoC cycling tests. As shown, in these cases, the SLI battery fails rapidly.

[0099] During conventional battery charging operations, for example as Figure 15 shown, concentrated sulfuric acid is generated on the electrode surface. Such concentrated acid is substantially heavier than the bulk acid between the plates and will thus sink to the bottom of the battery and stratify. If the battery is then fully charged, oxygen and hydrogen will carry the heavier acid upward. While operating in a partial state of charge, overcharging can no longer be relied upon to mix the acid. Therefore, an alternative mechanism for mixing the acid is needed.

[0100] One strategy is to utilize the vehicle's energy to mix the acid. When the vehicle accelerates or brakes, the acid sloshes back and forth, resulting in passive acid mixing. However, as shown using a computational fluid dynamics model Figure 16 when using a conventional SLI separator with uninterrupted ribs, this passive mixing does not occur. Assuming the worst-case scenario, i.e., a fully stratified case with water at the top and acid at the bottom, a 60-second lateral movement was simulated and a visualization output of the degree of mixing was generated. Starting with a standard uninterrupted rib SLI separator, after 60 seconds of movement, the acid is only slightly mixed outside the plates. The separator in the form of a serrated rib in the middle is a standard uninterrupted rib separator where the ribs are interrupted or serrated such that they are no longer an uninterrupted barrier to the movement of acid along the horizontal plane. Computer simulations show a small degree of mixing with the serrated rib separator. The ribs on the far left are the optimized serrated rib separators (e.g., Rip ) described in some embodiments herein. As shown, the acid that was originally at the bottom of the battery case is now being distributed upward. Thus, some of the separators described herein can reduce acid stratification under PSoC operating conditions by allowing passive mixing of the acid. However, NAM swelling under PSoC operating conditions affects this ability to passively mix.

[0101] The inventors have found that one way to minimize the effect of NAM swelling is to maximize the elasticity of the separator, thereby reducing the likelihood that the NAM will deflect the porous backweb into the PAM. A particular way to increase the elasticity of the separator is to increase the thickness of the porous membrane backweb. However, this also increases the resistance of the separator (just one detriment of a thicker backweb), which adversely affects the performance of the battery. The inventors have found that increasing the number of contact points between the separator and the positive electrode serves to stiffen the backweb between the contact points. Increasing the number of ribs to achieve this also increases the contact area between the separator and the positive electrode. It is believed that minimizing the contact area can reduce the resistance of the separator and open up more electrode surface area for the electrolyte to undergo the electrochemical reactions that provide the battery function. It is also believed that the reduced contact area reduces the chance of dendrite formation through the separator and causing an electrical short. The problem of dendrite formation is discussed below. A further goal is to maximize the mixing of the electrolyte or acid in the battery used in motion to minimize the effect of acid stratification. Further, uninterrupted ribs do not promote acid mixing for the purpose of reducing acid stratification.

[0102] The inventors have found that, as a selected exemplary preferred embodiment, the separator can be provided with an elastic means to resist or mitigate the backweb deflection under the forces and pressures imposed by NAM swelling (which results in acid starvation) by maximizing the number of contact points while minimizing the contact area between the separator and the adjacent electrode. The inventors have found that another selected exemplary embodiment can provide a separator with an acid mixing means to reduce, mitigate or reverse the effect of acid stratification by maximizing the number of discrete contact points between the separator and the adjacent electrode. Another selected exemplary embodiment can provide a separator with a dendrite mitigation means to reduce or slow the growth of lead sulfate (PbSO 4 ) dendrites. The inventors have determined that such elastic means, acid mixing means and dendrite mitigation means can be addressed, achieved or at least partially addressed and / or achieved through the design of the rib structure. Accordingly, the selected embodiments described herein rely on the rib structure in order to balance these parameters to achieve the desired goals, provide elastic means, acid mixing means and dendrite mitigation means, and / or 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.

[0103] Now referring to Figure 8A and Figure 8B , which shows a typical commercially available separator 300 disposed between a positive electrode plate 200 and a negative electrode plate 201. Although not shown, it is assumed that the assembly is located within the battery and immersed in the electrolyte 104. For simplicity, the negative ribs are omitted. Figure 8A Depicts a porous membrane 302 having a face 302p facing the positive electrode plate 200 and a face 302n facing the negative electrode plate 201. AsFigure 8B As shown, cycling of the battery causes the active material in plates 200, 201 to swell and deflects the porous membrane 302 between ribs 304. As shown, the negative active material of the negative plate 201 swells and causes the separator to deflect towards the positive plate 200. At the same time, the positive active material of the positive plate 200 swells and, in combination with the swelling of the negative plate, squeezes most of the electrolyte 104 out of the space between the electrode plates 200, 201. This condition is known as acid starvation or electrolyte starvation and severely damages the life and performance of the lead acid battery.

[0104] Now refer to Figure 8C and Figure 8D , which shows an exemplary improved and inventive separator 300 of the present invention that alleviates the acid starvation typically allowed by previously known battery separators. As Figure 8A and 8B shown, which shows the main or positive ribs 304 of a typical commercially available separator 300, which has a first rib spacing (first spacing 正极肋 , 1 st Spacing PosRib ) and a first rib tip width (first tip width 正极 , 1 st TipW Pos ). Now refer to Figure 8C and 8D of the exemplary inventive separator 300, the positive ribs 304 are shown as having a second rib spacing (second spacing 正极肋 , 2 nd Spacing PosRib ) and a second rib tip width (second tip width 正极 , 2 nd TipW Pos ). Although not drawn to scale, the second spacing and second tip width are shorter or smaller in size than the first spacing and first tip width. This minimizes the contact area between the separator 300 of the present invention and the adjacent electrodes 200, 201 while maximizing the number of discrete contact points. As can be seen in Figure 8C , compared to the conventional separator shown in Figure 8A and 8B , the swollen electrodes 200, 201 do not deflect the separator and squeeze out as much electrolyte between the electrodes. Now refer to Figure 8D , which shows Figure 8CThe separator 300 of the present invention is substantially similar to the separator described above, but has a negative electrode rib 305 that further separates the porous membrane 302 from the negative electrode 201. This completely prevents or at least mitigates the deflection of the porous membrane 302 and further reduces the impact of acid deficiency. As described herein, ribs 304 and 305 can have different heights and widths and do not have to be dependent on each other. Further, the positive electrode rib 304 can be spaced apart from the negative electrode rib 305 at different intervals.

[0105] Reference Figure 9A and Figure 9B , a specific exemplary embodiment of the separator 300 of the present invention is provided with an array of positive electrode ribs, which may be provided with a rib base that extends the length of the separator in the machine direction md. Then, spaced teeth, discontinuous peaks, or other protrusions (teeth) can extend from the surface of the rib base such that the teeth protrude on the surface of the underlying porous membrane backweb. In addition, the rib base can be wider than the teeth themselves. The positive electrode ribs are substantially parallel to each other at a typical spacing of about 2.5 mm to about 6.0 mm (spacing 正极肋 , Spacing PosRib ), with a typical spacing of about 3.5 mm. The height of the positive electrode rib (tooth plus bottom portion, height 正极肋 , Height PosRib ) measured from the surface of the porous membrane backweb can be about 10 μm to about 2.0 mm, with a typical height of about 0.5 mm. The exemplary rib teeth of adjacent rows of ribs can be substantially in a straight line with each other. However, as Figure 9B is drawn, the exemplary teeth in the first row can be offset from the ribs in the adjacent second row and be completely or partially out of phase with the ribs in the adjacent row. As shown, the teeth are completely out of phase from the first row to the second row. The positive electrode rib teeth can be spaced apart at a pitch of about 3.0 mm to about 6.0 mm (pitch 齿 , Pitch Tooth ) in the machine direction md of the separator, with a typical spacing of about 4.5 mm.

[0106] Continuing to refer to Figure 9A and Figure 9B , the exemplary negative electrode ribs are depicted as being substantially parallel to the cross machine direction cmd of the separator 300. However, as an alternative, they can also be substantially parallel to the machine direction md. The depicted exemplary negative electrode ribs are shown as uninterrupted and substantially straight. However, as an alternative, they can also be toothed in a manner generally similar to the positive electrode ribs. The negative electrode ribs can be spaced apart at a spacing of about 10 μm to about 10.0 mm (spacing 负极肋 , Spacing NegRib), the preferred spacing is between about 700 μm and about 800 μm, and the more preferred nominal spacing is about 740 μm. The height of the negative electrode ribs measured from the back net surface (height 负极肋 , Height NegRib ) can be from about 10 μm to about 2.0 mm.

[0107] It should be noted that, as an alternative, the positive electrode ribs can also be arranged in the exemplary battery such that they contact the negative electrode plate. Similarly, as an alternative, the negative electrode ribs can also be placed in the exemplary battery such that they contact the positive electrode plate. It should be further noted that both the positive electrode ribs and / or the negative electrode ribs can be configured to be similar to Figure 9A and 9B the positive electrode ribs shown. Additionally, both the positive electrode ribs and the negative electrode ribs can be substantially aligned in the processing direction, across the processing direction; or one group in the processing direction and the other group across the processing direction.

[0108] Table 1 below details the rib numbers and surface contact area percentages of four separators (one exemplary inventive separator and three control separators) of 162 mm × 162 mm (262 cm 2 ). The particular inventive separator is provided with 43 toothed ribs evenly spaced along the entire width of the separator across the processing direction. The teeth of the positive electrode ribs on the exemplary inventive separator contact 3.8% of the 262 cm 2 on the positive electrode. The details of the control separators are further detailed in Table 1. It should be understood that Control Separators #1, #2, and #3 are typical commercially available separators currently used in flooded lead-acid batteries and currently available on the market.

[0109] Table 1

[0110] Separator Rib [quantity (configuration)] Contact area (% of total area) Inventive separator 43 (toothed ribs) 3.8％ Control #1 22 (continuous ribs) 4.8％ Control #2 18 (continuous ribs) 3.9％ Control #3 11 (continuous ribs) 2.9％

[0111] As described above, the inventors have found that by minimizing the contact area while maximizing the number of contact points, the goal of improving the separator elasticity while keeping the resistance controllable is achieved. Additionally, the toothed design helps to promote acid mixing by taking advantage of any movement the battery may undergo. The teeth of the separator ribs can be spaced about 2.5 mm to about 6.0 mm from the nearest adjacent teeth. The inventors have found that the preferred, non-limiting distance between adjacent teeth is about 4.2 mm. Additionally, the teeth offset from adjacent rows being completely out of phase helps to promote acid mixing. The inventors have also found that the bottom portion helps to make the back net rigid enough to provide elasticity for NAM swelling.

[0112] Referring to Figure 10A and Figure 10B, which shows an exemplary electrode surface that has a supported area and an unsupported area from a separator (not shown) of the present invention. Figure 10A shows most of the electrode surface, while Figure 10B shows a close-up detail view of the electrode surface. As can be seen from Figure 10B , points A, B, and C show different positions on the ribs or rib teeth, which have an unsupported distance radius around them (i.e., the distance between one support position and the nearest adjacent support position). As described above, this unsupported distance can be from about 2.5 mm to about 6.0 mm.

[0113] In a particular exemplary embodiment, the positive electrode ribs can have a bottom portion ( Figure 9A and 9B the rib bottom in

[0114] ). If present, it can have an average bottom height of about 5 μm to about 200 μm. For example, the average bottom height can be greater than or equal to about 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, or 200 μm. Additionally, if present, it can have an average bottom width that is about 0.0 μm to about 50 μm wider than the tooth width. For example, the average bottom width can be greater than or equal to about 0.0 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm wider than the tooth width.

[0114] In a particular exemplary embodiment, the positive electrode ribs can be teeth or toothed ribs. If present, it can have an average tip length TipL of about 50 μm to about 1.0 mm Tooth (tip length 齿 ). For example, the average tip length can be greater than or equal to about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm. As an alternative, it can be not greater than or equal to 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

[0115] In some preferred embodiments, at least a portion of the teeth or toothed ribs can have an average tooth bottom length BaseL of about 50 μm to about 1.0 mm Tooth (bottom length 齿)。For example, the average bottom length of the teeth 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. As an alternative, it can be not greater than or equal to about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm or 50 μm.

[0116] In some preferred embodiments, at least a portion of the teeth or toothed ribs can have an average height (bottom portion height plus tooth height) of from about 50 μm to about 1.0 mm Height PosRib (height 正极肋 )。For example, the average height can be about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1.0 mm. Alternatively, it can be not greater than or equal to about 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm or 50 μm.

[0117] In some preferred embodiments, at least a portion of the teeth or toothed ribs can have an average center-to-center pitch of from about 100 μm to about 50 mm within columns in the processing direction. For example, the average center-to-center pitch can be greater than or equal to about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1.0 mm and in similar increments up to 50 mm. Alternatively, it can be not greater than or equal to about 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1.0 mm and in similar increments up to 50 mm. Additionally, adjacent columns of teeth or toothed ribs can be arranged in the same position or offset in the processing direction. In an offset configuration, adjacent teeth or toothed ribs are arranged in different positions in the processing direction.

[0118] In some selected preferred embodiments, at least a portion of the teeth or toothed ribs may have an average height to base width ratio of from about 0.1:1.0 to about 500:1.0. For example, the average height to base width ratio may be approximately 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 not greater than or equal to about 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.

[0119] In some preferred embodiments, at least a portion of the teeth or toothed ribs may have an average base width to tip width ratio of from about 1,000:1.0 to about 0.1:1.0. For example, the average base width to tip width ratio may be about 0.1:1.0, 1.0:1.0, 2:1.0, 3:1.0, 4:1.0, 5:1.0, 6:1.0, 7:1.0, 8:1.0, 9:1.0, 10:1.0, 15:1.0, 20:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1.0, 450:1.0, 500:1.0, 550:1.0, 600:1.0, 650:1.0, 700:1.0, 750:1.0, 800:1.0, 850:1.0, 900:1.0, 950:1.0 or 1000:1.0. Alternatively, the average base width to tip width ratio may be not greater than about 1,000:1.0, 950:1.0, 900:1.0, 850:1.0, 800:1.0, 750:1.0, 700:1.0, 650:1.0, 600:1.0, 550:1.0, 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 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.

[0120] Backsheet thickness

[0121] In some embodiments, the porous separator membrane may have a backsheet thickness of from about 50 μm to about 1.0 mm. For example, the backsheet 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 backsheet thickness may be no greater than 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. Although in certain embodiments, a very thin flat backsheet thickness of 50 μm or less is provided, for example, between about 10 μm and about 50 μm thick.

[0122] The total thickness of the exemplary separator (backsheet thickness and the height of the positive and negative ribs) is typically in the range of from about 250 μm to about 1.0 mm. The total thickness of the separator used in automotive start / stop batteries is typically from about 250 μm to about 1.0 mm. The total thickness of the separator used in industrial traction start / stop batteries is typically from about 1.0 mm to about 4.0 mm.

[0123] Composition

[0124] In certain exemplary embodiments, the improved separator may include a porous membrane made of the following materials: natural or synthetic substrates, processing plasticizers, fillers, one or more natural or synthetic rubbers or latexes, and one or more other additives and / or coatings, and / or the like.

[0125] Base material

[0126] In certain embodiments, exemplary natural or synthetic substrates may include: polymers, thermoplastic polymers, phenolic resins, natural or synthetic rubbers, 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. In principle, exemplary thermoplastic polymers may include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. In certain preferred embodiments, exemplary thermoplastic polymers may include vinyl compounds and polyolefins. In certain embodiments, vinyl compounds 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, but preferably polyethylene. In certain embodiments, exemplary natural or synthetic rubbers may include, for example, latex, non-crosslinked or crosslinked rubbers, rubber crumbs, or ground rubber, and any combination thereof.

[0127] In addition, it has been observed that when antimony (Sb) is present in the NAM and / or the negative electrode, the NAM swelling is reduced. Accordingly, an antimony coating can be provided on the separator or an antimony additive can be incorporated into the separator composition.

[0128] Polyolefin

[0129] In certain embodiments, the porous membrane layer preferably comprises a polyolefin, particularly polyethylene. Preferably, the polyethylene is high molecular weight polyethylene (HMWPE, e.g., polyethylene having a molecular weight of at least 600,000). Even more preferably, the polyethylene is ultra-high molecular weight polyethylene (UHMWPE). Exemplary ultra-high molecular weight polyethylene can have a molecular weight of at least 1,000,000, particularly greater than 4,000,000, and most preferably 5,000,000 to 8,000,000, where the molecular weight is measured by a viscometer and calculated by the Margolie equation. Additionally, exemplary UHMWPE can have a standard load melt index that is essentially zero (0), as measured according to ASTM D 1238 (Condition E) using a standard load of 2,160 g. Further, exemplary UHMWPE can have a viscosity value of not less than 600 ml / g, preferably not less than 1,000 ml / g, more preferably not less than 2,000 ml / g, and most preferably not less than 3,000 ml / g, which is determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C.

[0130] Rubber

[0131] The novel separator disclosed herein can comprise latex and / or rubber. As used herein, "rubber" shall describe rubber, latex, natural rubber, synthetic rubber, cross-linked or uncross-linked rubber, cured or uncured rubber, rubber crumbs or ground rubber, or mixtures thereof. Exemplary natural rubber can include blends of one or more polyisoprenes, which are available from various suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber can be cross-linked rubber or non-cross-linked rubber; in certain preferred embodiments, the rubber is non-cross-linked rubber. In certain embodiments, the rubber can be a blend of cross-linked rubber and non-cross-linked rubber.

[0132] Plasticizer

[0133] In certain embodiments, exemplary processing plasticizers can include processing oils, petroleum, paraffin-based mineral oils, mineral oils, and any combination thereof.

[0134] Filler

[0135] The separator can contain fillers having a high structural morphology. Exemplary fillers can include: silica, dry-processed finely divided silica, precipitated silica, amorphous silica, highly friable silica, alumina, talc, fish meal, fish bone meal, carbon, carbon black, and the like, and combinations thereof. In certain preferred embodiments, the filler is one or more silicas. High structural morphology refers to an increased surface area. The filler can have a high surface area, for example, greater than 100 m 2 / g, 110 m 2 / g, 120 m 2 / g, 130 m 2 / g, 140 m 2 / g, 150 m 2 / g, 160 m 2 / g, 170 m 2 / g, 180 m 2 / g, 190 m 2 / g, 200 m 2 / g, 210 m 2 / g, 220 m 2 / g, 230 m 2 / g, 240 m 2 / g or 250 m 2 / g. In some embodiments, the filler (such as silica) can have 100 - 300 m 2 / g, 125 - 275 m 2 / g, 150 - 250 m 2 / g or preferably 170 - 220 m 2The surface area per gram. The surface area can be evaluated using the multi-point BET nitrogen surface area obtained by TriStar3000TM. The high structure morphology allows the filler to absorb more oil during the manufacturing process. For example, a filler with a high structure morphology has a high level of oil absorption, such as greater than about 150 ml / 100 g, 175 ml / 100 g, 200 ml / 100 g, 225 ml / 100 g, 250 ml / 100 g, 275 ml / 100 g, 300 ml / 100 g, 325 ml / 100 g, or 350 ml / 100 g. In some embodiments, the filler (such as silica) can have an oil absorption of 200 - 500 ml / 100 g, 200 - 400 ml / 100 g, 225 - 375 ml / 100 g, 225 - 350 ml / 100 g, 225 - 325 ml / 100 g, preferably 250 - 300 ml / 100 g. In some cases, a silica filler with an oil absorption of 266 ml / 100 g is used. Such a silica filler has a water content of 5.1%, a BET surface area of 178 m 2 / g, an average particle size of 23 μm, a sieve residue on a 230 - mesh sieve of 0.1%, and a bulk density of 135 g / L.

[0136] When forming an exemplary lead - acid battery separator of the type shown herein, silica having a relatively high oil absorption and a relatively high affinity for a plasticizer (such as mineral oil) becomes desirably dispersed in a mixture of a polyolefin (such as polyethylene) and the plasticizer. In the past, when a large amount of silica was used to manufacture such separators or membranes, some separators suffered from poor dispersion caused by silica aggregation. In at least the specific inventive separators shown and described herein, since there are few silica aggregates or agglomerates that inhibit the movement of polyolefin molecules when cooling the molten polyolefin, a polyolefin such as polyethylene forms a shish - kebab structure. All of these contribute to improving the ionic permeability through the resulting separator membrane, and the formation of the shish - kebab structure or morphology means that a separator with a lower overall ER and maintained or even increased mechanical strength is produced.

[0137] In some selected embodiments, the filler (such as silica) has an average particle size of no greater than 25 μm, in some cases no greater than 22 μm, 20 μm, 18 μm, 15 μm, or 10 μm. In some cases, the average particle size of the filler particles is about 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 can fall within the above - mentioned sizes. However, the initial silica used as a raw material can occur in the form of one or more aggregates and / or agglomerates and can have a size of about 200 μm or greater.

[0138] In some preferred embodiments, the silica used to fabricate the separator of the present invention has an increased number or quantity of surface silanol groups (surface hydroxyl groups) compared to the silica fillers previously used to fabricate lead-acid battery separators. For example, the silica fillers that can be used in conjunction with the specific preferred embodiments herein can be those that have at least 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 the known silica fillers used to fabricate known polyolefin lead-acid battery separators.

[0139] The ratio of silanol groups (Si-OH) to silicon (Si) element, (Si-OH) / Si, can be determined, for example, as follows.

[0140] 1. Freeze-crush a polyolefin porous membrane (wherein a specific membrane of the present invention contains a specific type of oil-absorbing silica according to the present invention), and prepare a powdered sample for solid-state nuclear magnetic resonance spectroscopy ( 29 Si-NMR).

[0141] 2. Perform 29 Si-NMR on the powdered sample and observe the spectrum, which includes the spectral intensity of Si directly bonded to hydroxyl groups (spectrum: Q 2 and Q 3 ) and the spectral intensity of Si directly bonded only to oxygen atoms (spectrum: Q 4 ), where the molecular structure of each NMR peak spectrum can be classified as follows:

[0142] ·Q 2 : (SiO) 2 -Si*-(OH) 2 : Having two hydroxyl groups

[0143] ·Q 3 : (SiO) 3 -Si*-(OH): Having one hydroxyl group

[0144] ·Q 4 : (SiO) 4 -Si*: All Si bonds are SiO

[0145] wherein Si* is the element proven by NMR observation.

[0146] 3. The conditions for observing 29 Si-NMR are as follows:

[0147] · Instrument: Bruker BioSpin Avance 500

[0148] · Resonance frequency: 99.36 MHz

[0149] · Sample amount: 250 mg

[0150] · NMR tube:

[0151] · Observation method: DD / MAS

[0152] · Pulse width: 45°

[0153] · Repetition time: 100 sec

[0154] · Scans: 800

[0155] · Magic angle spinning: 5000 Hz

[0156] · Chemical shift reference: Silicone rubber at -22.43 ppm

[0157] 4. Numerically separate the peaks of the spectrum and calculate the area ratios of the peaks belonging to Q 2 、Q 3 、Q 4 . Then, based on the ratios, calculate the molar ratio of the hydroxyl groups (-OH) directly bonded to Si. The conditions for numerical peak separation are as follows:

[0158] · Fitting region: -80 to -130 ppm

[0159] · Initial peak tops: Respectively, Q 2 at -93 ppm, Q 3 at -101 ppm, Q 4 at -111 ppm

[0160] · Initial maximum half-peak widths: Respectively, Q 2 at 400 Hz, Q 3 at 350 Hz, Q 4 at 450 Hz

[0161] · Gaussian function ratio: 80% initially, 70 to 100% during fitting.

[0162] 5. Calculate the peak area ratios (total of 100) of Q 2 、Q 3 、Q 4 from each peak obtained by fitting. The NMR peak area corresponds to the number of molecules of each silicate bond structure (thus, for the Q 4 NMR peak, there are 4 Si-O-Si bonds in this silicate structure; for the Q 3 NMR peak, there are 3 Si-O-Si bonds and 1 Si-OH bond in this silicate structure; for the Q 2NMR peaks, there are two Si-O-Si bonds and two Si-OH bonds within the silicate structure). Thus, Q 2 and Q 3 and Q 4 are each multiplied by two (2), one (1), and zero (0), respectively, for the number of each hydroxyl group (-OH). These three results are added together. This total value shows the molar ratio of hydroxyl groups (-OH) directly bonded to Si.

[0163] In certain embodiments, the silica may have a molecular ratio of OH to Si groups measured by 29 Si-NMR, which may be in the range of about 21:100 to 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 greater.

[0164] In some selected embodiments, using the above fillers enables a greater proportion of processing oil to be used in the extrusion step. Since the porous structure in the separator is partially formed by removing the oil after extrusion, a higher initial oil absorption leads to a higher porosity or a higher void volume. And the processing oil is an integral part of the extrusion step, and the oil is a non-conductive component in the separator. The residual oil in the separator can protect the separator from oxidation when it contacts the positive electrode. In the manufacture of conventional separators, the precise amount of oil in the processing step can be controlled. Generally, conventional separators are manufactured using 50 - 70 wt% of processing oil, 55 - 65 wt% in some embodiments, 60 - 65 wt% in some embodiments, and about 62 wt% of processing oil in some embodiments. It has been known that reducing the oil to below about 59% can cause combustion due to increased friction with the extruder components. However, increasing the oil content far above the specified amount may cause shrinkage during the drying stage, resulting in dimensional instability. Although previous attempts to increase the oil content have led to shrinkage or reduction of pores during oil removal, the separators prepared as disclosed herein exhibit minimal shrinkage and reduction, if any, during oil removal. Thus, the porosity can be increased without affecting the pore size and dimensional stability, thereby reducing the resistance.

[0165] In certain selected embodiments, the use of the above fillers can reduce the final oil concentration in the finished separator. Since oil is a non-conductor, reducing the oil content can increase the ionic conductivity of the separator and contribute to reducing the ER of the separator. Thus, a separator with a reduced final oil content can have increased efficiency. In certain selected embodiments, a separator is provided having a final processed oil content (by weight) of less than 20%, for example, between about 14% and 20%, and in some specific embodiments, less than 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6% or 5%.

[0166] The filler can further reduce the so-called hydration spheres of electrolyte ions, enhancing their transmembrane transport and thus again reducing the overall resistance or ER of the battery (such as an enhanced flooded battery) or system.

[0167] One or more fillers can comprise various substances (e.g., polar substances such as metals) that facilitate the flow of electrolyte and ions through the separator. When such a separator is used in a flooded battery (such as an enhanced flooded battery), this also results in a reduction in the overall resistance.

[0168] Brittleness

[0169] In certain selected embodiments, the filler can be alumina, talc, silica or a combination thereof. In some embodiments, the filler can be precipitated silica, and in some embodiments, the precipitated silica is amorphous silica. In some embodiments, aggregates and / or agglomerates of silica are preferably used, which allow the filler to be well dispersed throughout the separator, thereby reducing tortuosity and resistance. In certain preferred embodiments, the filler (e.g., silica) is characterized by a high level of brittleness. Good brittleness improves the dispersion of the filler throughout the polymer during the extrusion of the porous membrane, increases porosity, and thus increases the overall ionic conductivity through the separator.

[0170] Brittleness can be measured as the ability, tendency or propensity of silica particles or material (aggregates or agglomerates) to break down into smaller sized and more dispersible particles, fragments or components. The novel silica of the present invention is more brittle than standard silica (being broken down into smaller fragments after 30 seconds and 60 seconds of sonication). For example, and as Figure 11As shown, the new silica of the present invention can 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, at 30 seconds of sonication, the size (diameter) of 50% of the silica particles is reduced by more than 50%, and at 60 seconds, the size (diameter) is reduced by more than 75%. Therefore, a possible preferred definition of "high brittleness" can be that the average size (diameter) of the silica particles is reduced by at least 50% at 30 seconds of sonication and at least 75% at 60 seconds of sonication (or during the processing of resin-silica mixing to form a film). In at least certain embodiments, it may be preferred to use more brittle silica, and even more preferably brittle and multimodal silica, such as bimodal or trimodal in brittleness. For example, traditional standard silica is unimodal in brittleness or particle size distribution, while the new silica of the present invention appears to be more brittle, bimodal (two peaks) at 30 seconds of sonication, and trimodal (three peaks) at 60 seconds of sonication. One or more of these brittle and multimodal particle size silicas can provide enhanced membrane and separator performance.

[0171] Separators with a higher final porosity can be produced using a filler having one or more of the above characteristics. The separators disclosed herein can have a final porosity greater than 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%. The porosity can be measured by gas adsorption method. BS-TE-2060 can be used to measure the porosity.

[0172] In some selected embodiments, the porous separator can have a greater proportion of larger pores while maintaining an average pore diameter not greater than about 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, or 0.1 μm.

[0173] According to at least one embodiment, the separator is made by mixing polyethylene (such as ultra-high molecular weight polyethylene (UHMWPE)) with processing oil and filler and any desired additives. According to at least one other embodiment, the separator is made by mixing ultra-high molecular weight polyethylene (UHMWPE) with processing oil and talc. According to at least one other embodiment, the separator is made by mixing UHMWPE with processing oil and silica (such as precipitated silica, such as amorphous precipitated silica). Thereafter, the additives can be applied to the separator by one or more of the above techniques.

[0174] In addition to reducing resistance and increasing cold start current, the preferred separator is also designed to provide other advantages. In terms of assembly, the separator is more easily passed through processing equipment, and thus the manufacturing efficiency is higher. To prevent short circuits during high-speed assembly and in subsequent use, the separator has excellent puncture strength and oxidation resistance when compared to standard PE separators. Combined with the reduced resistance and increased cold start current, battery manufacturers are likely to find that using these new separators, their batteries have improved and durable electrical performance.

[0175] Conductive layer

[0176] In certain embodiments, the separator may include performance enhancing additives in the form of nucleating additives and / or coatings. The nucleating additives may preferably be stable in the electrolyte of the battery and may further be dispersed in the electrolyte.

[0177] The inventors hypothesize that when charging the battery, smaller lead sulfate crystals are more likely to return to solution compared to larger crystals. It is believed that providing nucleation sites provides a starting point for crystal formation. Further, many nucleation sites can provide many locations for crystal formation, thereby spreading the total amount of lead sulfate into a large number of smaller crystals rather than a smaller number of larger crystals. Thereafter, during the charging cycle of the battery, these smaller crystals will be more likely to return to solution and thus hinder the growth of dendrites. The inventors have found a variety of nucleating additives for the separator, such as carbon and barium sulfate (BaSO 4 )), as exemplary means for providing these nucleation sites. In addition to providing nucleation sites, carbon can also improve the charge acceptance of the battery and increase the battery capacity.

[0178] Another benefit provided by carbon is to improve charge acceptance. One hypothesis of the inventors is that highly conductive carbon particles provide an electron conduction path to the active material and thus improve the utilization of the active material. Another hypothesis of the inventors is that carbon increases the separator capacity and thus increases the capacity of the entire battery system.

[0179] For example as Figure 25 and Figure 26 shown in, the conventional method is to add a relatively small percentage of carbon to the negative electrode active material. However, the disadvantage of this method is that most of the carbon is not close to the surface where lead sulfate crystals are formed, so little of this material can be truly used for its purpose.

[0180] In some embodiments described herein, a nucleating additive, such as carbon, is coated on the surface of the separator that will contact the electrode. This places the nucleating material directly on the interface where crystal growth actually occurs.

[0181] Exemplary forms of the nucleating additive and / or coating can be or include carbon, such as carbon, conductive carbon, graphite, artificial graphite, activated carbon, carbon paper, acetylene black, carbon black, high surface area carbon black, graphene, high surface area graphene, keitjen black, carbon fiber, carbon filament, carbon nanotube, open-cell carbon foam, carbon mat, carbon felt, carbon buckminsterfullerene (buckyball), aqueous carbon suspension, and combinations thereof. In addition to these various forms of carbon, the nucleating additive and / or coating can also include or contain barium sulfate (BaSO 4 ).

[0182] The nucleating coating can be applied to the finished separator by means such as slurry coating, slot die coating, spraying, curtain coating, inkjet printing, screen printing, or by vacuum deposition or chemical vapor deposition (CVD). In addition, the additive and / or coating can be provided in the form of carbon paper, which can be woven or non-woven, and is located between and in intimate contact with the separator and one or more electrodes.

[0183] The nucleating additive and / or coating can be within the separator or on one or both electrode-facing surfaces of the separator. Typically, the coating or layer of the nucleating additive can be only on the surface facing the negative electrode. However, it can be on the surface facing the positive electrode or on both surfaces.

[0184] In certain embodiments, the nucleating additive can be added to the extrusion blend of the substrate and co-extruded with the separator or as a layer on the separator. When included in the extrusion mixture, the nucleating additive can replace part of the silica filler, up to 5% to 75% by weight. For example, the nucleating additive can be about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or about 75% by weight. In other exemplary embodiments, the nucleating additive can be no greater than about 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or about 5% by weight.

[0185] A conductive layer may be disposed on an exemplary battery separator. The conductive layer may preferably be adapted to contact the positive electrode of the battery. The conductive layer may be used to provide a new path for current to enter and exit the positive electrode. The conductive layer may be made of any conductive material, including but not limited to aluminum oxide, lead, gold, antimony, arsenic, zinc, barium, beryllium, lithium, magnesium, nickel, aluminum, silver, tin, carbon, and their combination alloys, or carbon fibers, graphite, carbon, carbon and zinc, carbon nanotubes, buckminsterfullerenes (or buckyballs), and their combinations. Carbon nanotubes or buckyballs may be dispersed in a medium with a binder and coated on the battery separator. The conductive layer may be made of any conductive material that is more corrosion-resistant than the positive electrode conductor, whereby the conductive layer can act as the positive electrode conductor when the conductivity of the positive electrode conductor deteriorates. The conductive layer may be a lead-based alloy having 0.8% to 1.17% tin and greater than zero (0) to 0.015% silver. The conductive layer may be a lead-based alloy having 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 tapes, screens, foils, wires, filaments, coatings, etc., or combinations thereof. The conductive layer may be of any thickness, for example, a thickness of about 3 μm. The conductive layer may be disposed on the battery separator by any means, including but not limited to adhesion, heat melting, coating, etc. The conductive layer may be as described in U.S. Patent No. 9,564,623, which is incorporated herein by reference in its entirety.

[0186] Resistance

[0187] In certain selected embodiments, the disclosed separators exhibit a reduced resistance, e.g., not greater than about 200 mΩ·cm 2 、180 mΩ·cm 2 、160 mΩ·cm 2 、140 mΩ·cm 2 、120 mΩ·cm 2 、100 mΩ·cm 2 、80 mΩ·cm 2 、60 mΩ·cm 2 、50 mΩ·cm 2 、40 mΩ·cm 2 、30 mΩ·cm 2 or 20 mΩ·cm 2 resistance. In different embodiments, compared to known separators of the same thickness, the separators described herein exhibit an ER drop of about 20% or more. For example, a known separator may have an ER value of 60 mΩ·cm 2 ; thus, a separator according to the present invention of the same thickness will have an ER value of less than about 48 mΩ·cm 2 .

[0188] In order to test the sample separator for ER test evaluation according to the present invention, the test separator must first be prepared. For this purpose, the sample separator is preferably immersed in a deionized water bath, and then the water is boiled. After 10 minutes in the boiling deionized water bath, the separator is removed. After removal, the excess water on the separator is shaken off, and then it is placed in a sulfuric acid bath with a specific gravity of 1.280 at 27°C ± 1°C. The separator is immersed in the sulfuric acid bath for 20 minutes. Subsequently, the separator is ready for resistance testing.

[0189] Oxidation stability

[0190] In certain selected embodiments, the exemplary separators may be characterized as having improved and higher oxidation resistance. Oxidation resistance is measured by measuring the elongation of a sample separator specimen in the cross-machine direction after long-term exposure to the environment within a lead-acid battery, including acidic electrolytes and temperature fluctuations. For example, the exemplary separator may have an elongation of about 100% or more, 150% or more, 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more at 40 hours. In certain embodiments, the exemplary separator may have a preferred oxidation resistance or elongation of about 100% or more at 40 hours. In addition, the exemplary separator may have an elongation of about 200% or more, 250% or more, 300% or more, 350% or more, 400% or more, 450% or more, or 500% or more at 20 hours. In certain embodiments, an exemplary separator may have a preferred oxidation resistance or elongation of about 200% or more at 20 hours.

[0191] To test the oxidation resistance of the sample, the sample specimen 1200 of the exemplary separator was first cut into Figure 12A The sample 1200 is then placed in a Figure 12B and 12C In the sample holder 1220 generally shown in FIG.

[0192] At time = 0 hours, the first set of dried samples were tested for percent elongation to break. Elongation is based on the Figure 12A The distance between points A and B is 50 ± 2 mm. For example, if the sample breaks with points A and B stretched to 300% of their distance, the final distance between A and B will be 150 ± 6 mm.

[0193] The elongation rate test is designed to simulate long-term exposure to the electrolyte in a cycling battery in a shortened time. First, the sample 1200 is completely immersed in isopropyl alcohol, drained, and then immersed in water for 1 to 2 seconds. After that, the sample is immersed in the electrolyte solution. The solution is prepared as follows: 360 ml of sulfuric acid with a specific gravity of 1.28, 35 ml of sulfuric acid with a specific gravity of 1.84, and 105 ml of 35% hydrogen peroxide are added in sequence. The solution is maintained at 80 °C, and the sample is immersed in the solution for a long time. The elongation rate of the sample can be tested at regular time intervals (such as 20 hours, 40 hours, 60 hours, 80 hours, etc.). To test at these time intervals, the sample 1200 is taken out of the electrolyte bath at 80 °C and placed under warm running water until the acid is removed. Then the elongation rate can be tested.

[0194] According to at least selected embodiments, the present disclosure or invention is directed to improved battery separators, low ER or high conductivity separators, improved lead-acid batteries (such as flooded lead-acid batteries), high conductivity batteries, and / or improved vehicles including such batteries and / or methods of manufacturing or using such separators or batteries, and / or combinations thereof. According to at least specific embodiments, the present disclosure or invention is directed to improved lead-acid batteries that incorporate improved separators and exhibit increased conductivity.

[0195] The antioxidant properties of exemplary separators can also be evaluated after a comprehensive service life test (such as the comprehensive service life test of SAE-J2801 - 12V automotive batteries).

[0196] Puncture resistance

[0197] In certain selected embodiments, exemplary separators can be characterized by improved puncture resistance. For example, a puncture resistance of about 9 N or higher, 9.5 N or higher, 10 N or higher, 10.5 N or higher, 11 N or higher, 11.5 N or higher, 12 N or higher, 12.5 N or higher, 13 N or higher, 13.5 N or higher, 14 N or higher, 14.5 N or higher, 15 N or higher, 15.5 N or higher, 16 N or higher, 16.5 N or higher, 17 N or higher, 17.5 N or higher, 18 N or higher, 18.5 N or higher, 19 N or higher, 19.5 N or higher, or 20 N or higher. In certain embodiments, exemplary separators can preferably be defined as having a puncture resistance of about 9 N to about 20 N or higher, or more preferably about 11 N to about 20 N or higher.

[0198] The puncture resistance can be measured as using Figure 13The force required for the tip 1300, generally depicted, to pierce the porous membrane. The piercing base on which the porous membrane is supported when the tip 1300 pierces the membrane can generally be described as a base having a straight hole with a diameter of 6.5 mm and a depth of 10 mm. The travel limit of the tip can be about 4 mm to about 8 mm below the surface of the piercing base. The piercing tip 1300 linearly translates into the membrane at a rate of approximately 5 mm / s.

[0199] Additive / surfactant

[0200] In certain embodiments, an exemplary separator may comprise one or more performance enhancing additives and / or coatings added to the separator or the porous membrane. The performance enhancing additives and / or coatings can be surfactants, wetting agents, colorants, antistatic additives and / or coatings, antimony inhibiting additives and / or coatings, ultraviolet light protecting additives and / or coatings, antioxidants and / or the like, and combinations thereof. In certain embodiments, the added and / or coated surfactant can be an ionic or non-ionic surfactant or a combination thereof.

[0201] It has been found that such performance enhancing additives and / or coatings reduce hydrogen evolution (H 2 ), and thus reduce water loss. This reduced water loss helps to mitigate grid corrosion. The inventors have noted that excessive grid corrosion tends to exacerbate grid warping.

[0202] Certain suitable surfactants can have an HLB value of less than 6, preferably less than 3. Using these particular suitable surfactants in conjunction with the inventive separators described herein can result in further improved separators that, when used in lead-acid batteries, can provide reduced water loss, reduced antimony poisoning, improved cycling, reduced floating current, reduced floating voltage, and / or the like or any combination thereof for the lead-acid battery. Suitable surfactants include surfactants such as alkyl sulfonates, alkyl aryl sulfonates, alkylphenol-ethylene oxide adducts, soaps, alkyl naphthalene sulfonates; one or more sulfosuccinates, such as anionic sulfosuccinates, dialkyl esters of sulfosuccinates; amino compounds (primary, secondary, tertiary amines or quaternary amines); block copolymers of ethylene oxide and propylene oxide, various polyethylene oxides, and salts of mono- and dialkyl phosphates. Additives can include non-ionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharides such as alkyl polyglycosides and their mixtures, amine ethoxylates, ethoxylated sorbitan fatty acid esters, silicone-based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphates of fatty acids, and sucrose esters.

[0203] In certain embodiments, the additive can be represented by a compound of formula (I)

[0204]

[0205] Wherein:

[0206] · R is a linear or non-aromatic hydrocarbon group having 10 to 4,200, preferably 13 to 4,200 carbon atoms, which may be interrupted by an oxygen atom;

[0207] · R 1 = H, or is preferably H, where k = 1 or 2;

[0208] · M is an alkali metal or alkaline earth metal ion, H + or NH 4 + , where not all of the variables M are H simultaneously + ;

[0209] · n = 0 or 1;

[0210] · m = 0 or an integer from 10 to 1,400; and

[0211] · x = 1 or 2.

[0212] In the compounds according to formula (I), the ratio of oxygen atoms to carbon atoms is in the range from 1:1.5 to 1:30, and m and n cannot both be 0. However, preferably only one of the variables n and m is not equal to 0.

[0213] The so-called non-aromatic hydrocarbon group means a radical that does not contain an aromatic group or that itself represents an aromatic group. The hydrocarbon group may be interrupted by an oxygen atom (i.e., contains one or more ether groups).

[0214] R is preferably a straight-chain or branched-chain aliphatic hydrocarbon group that may be interrupted by an oxygen atom. Saturated, non-crosslinked hydrocarbon groups are very particularly preferred. However, as described above, in certain embodiments, R may be aromatic-ring-containing.

[0215] By using the compounds according to formula (I) to produce battery separators, the separators can be effectively protected from oxidative damage.

[0216] Battery separators containing the compounds according to formula (I) are preferred, wherein:

[0217] · R is a hydrocarbon group having 10 to 180, preferably 12 to 75 and very particularly preferably 14 to 40 carbon atoms, which may be interrupted by 1 to 60, preferably 1 to 20 and very particularly preferably 1 to 8 oxygen atoms, particularly preferably the formula R 2 —[(OC 2 H 4 )p(OC 3 H 6 )q — of a hydrocarbon group, wherein:

[0218] o R 2 is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 carbon atoms, wherein R 2 can be linear or non-linear, such as containing an aromatic ring;

[0219] o P is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4; and

[0220] o q is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4;

[0221] o Compounds in which the sum of p and q is from 0 to 10, especially from 0 to 4, are particularly preferred;

[0222] · n = 1; and

[0223] · m = 0.

[0224] The formula R 2 —[(OC 2 H 4 ) p (OC 3 H 6 ) q — should be understood to also include those compounds in which the sequence of groups in the square brackets is different from that shown. For example, according to the present invention, compounds in which the radicals in the brackets are formed by alternating (OC 2 H 4 ) and (OC 3 H 6 ) groups are suitable.

[0225] It has been confirmed that additives in which R 2 is a straight-chain or branched-chain alkyl group having 10 to 20, preferably 14 to 18 carbon atoms are particularly advantageous. OC 2 H 4 preferably represents OCH 2 CH 2 , OC 3 H 6 represents OCH(CH 3 ) 2 and / or OCH 2 CH 2 CH 3 .

[0226] As preferred additives, mention may be made in particular of alcohols (p = q = 0, m = 0), primary alcohols being particularly preferred, fatty alcohol ethoxylates (p = 1 to 4, q = 0), fatty alcohol propoxylates (p = 0, q = 1 to 4) and fatty alcohol alkoxylates (p = 1 to 2, q = 1 to 4), the ethoxylates of primary alcohols being preferred. The fatty alcohol alkoxylates can be obtained, for example, by reaction of the corresponding alcohols with ethylene oxide or propylene oxide.

[0227] It has been found that additives of the m = 0 type which are insoluble or sparingly soluble in water and sulfuric acid are particularly advantageous.

[0228] Also preferred are additives which contain a compound according to formula (I), in which:

[0229] · R is an alkyl group having 20 to 4200, preferably 50 to 750 and very particularly preferably 80 to 225 carbon atoms;

[0230] · M is an alkali metal or alkaline earth metal ion, H + or in particular alkali metal ions such as Li + , Na + and K + or H + where not all of the variables M are simultaneously H + ;

[0231] · n = 0;

[0232] · m is an integer from 10 to 1400; and

[0233] · x = 1 or 2.

[0234] Salt additive

[0235] In certain embodiments, suitable additives can include, in particular, polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers, the acid groups of which are at least partially neutralized, for example preferably 40%, particularly preferably 80%. The percentages refer to the number of acid groups. Very particularly preferred are poly(meth)acrylic acids which are present entirely in salt form. Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn and ammonium (NR 4 where R is hydrogen or a carbon functional group). The poly(meth)acrylic acid can include polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylic acid is preferred, in particular with an average molar mass M wPolyacrylic acid having a molecular weight of 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, and especially preferably 1,000 to 4,000 g / mol. The molecular weights of poly(meth)acrylic acid polymers and copolymers are determined by measuring the viscosity (Fikentscher constant) of a 1% aqueous solution of the polymer neutralized with sodium hydroxide solution.

[0236] Equally suitable are copolymers of (meth)acrylic acid, especially copolymers containing, in addition to (meth)acrylic acid, ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and / or 2-ethylhexyl acrylate as comonomers. Copolymers containing at least 40 wt%, preferably at least 80 wt%, of (meth)acrylic acid monomers are preferred, this percentage being based on the acid form of the monomers or polymers.

[0237] For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide, especially sodium hydroxide, are particularly suitable. In addition, coatings and / or additives for strengthening the separator can include, for example, metal alkoxides, where the metal can be, by way of example only (not intended to be limiting), Zn, Na, or Al, such as sodium ethoxide by way of example only.

[0238] In some embodiments, the porous polyolefin porous membrane can include a coating on one or both sides of such a layer. Such a coating can include surfactants or other materials. In some embodiments, the coating can include, for example, one or more materials described in U.S. Patent No. 2012 / 0094183, which is incorporated herein by reference. Such a coating can, for example, reduce the overcharge voltage of the battery system, thereby extending the battery life by reducing grid corrosion and preventing drying out and / or water loss.

[0239] Ratio

[0240] In certain selected embodiments, a membrane can be prepared by combining about 5 - 15 wt% polymer (in some cases, about 10 wt% polymer such as polyethylene), about 10 - 75 wt% filler (such as silica, in some cases, about 30 wt% filler), and about 10 - 85 wt% processing oil (in some cases, about 60 wt% processing oil). In other embodiments, the filler content is reduced while the oil content is higher, for example, the oil is greater than about 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70% by weight. The filler:polymer ratio (by weight) can be approximately (or can be between approximately these specific ranges), 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) can range from about 1.5:1 to about 6:1, and in some cases, can range from 2:1 to 6:1, from about 2:1 to 5:1, from about 2:1 to 4:1, and in some cases, from about 2:1 to about 3:1. The amounts of filler, oil, and polymer are balanced for operability and desired separator properties such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flatness, etc.

[0241] According to at least one embodiment, the porous membrane can comprise UHMWPE mixed with processing oil and precipitated silica. According to at least one embodiment, the porous membrane can comprise UHMWPE mixed with processing oil, additives, and precipitated silica. The mixture can also comprise small amounts of other additives or reagents common in the separator art (e.g., surfactants, wetting agents, colorants, antistatic additives, antioxidants, and / or the like, and any combination thereof). In certain cases, the porous polymer layer can be a homogeneous mixture consisting of 8 - 100% volume of polyolefin, 0 - 40% volume of plasticizer, and 0 - 92% volume of inert filler material. A preferred plasticizer is petroleum. Since the plasticizer is the component most easily removed from the polymer - filler - plasticizer composition by solvent extraction and drying, it is useful in imparting porosity to the battery separator.

[0242] In certain embodiments, the porous membranes disclosed herein can comprise latex and / or rubber, which can be natural rubber, synthetic rubber, or mixtures thereof. Natural rubber can include blends of one or more polyisoprenes, which can be obtained from different suppliers. Exemplary synthetic rubbers include methyl rubber, polybutadiene, chloroprene rubber, butyl rubber, bromobutyl rubber, polyurethane rubber, epichlorohydrin rubber, polysulfide rubber, chlorosulfonated polyethylene, polynorbornene rubber, acrylate rubber, fluororubber, and silicone rubber, as well as copolymer rubbers such as styrene / butadiene rubber, acrylonitrile / butadiene rubber, ethylene / propylene rubber (EPM and EPDM), and ethylene / vinyl acetate rubber. The rubber can be crosslinked rubber or non-crosslinked rubber; in certain preferred embodiments, the rubber is non-crosslinked rubber. In certain embodiments, the rubber can be a blend of crosslinked rubber and non-crosslinked rubber. The rubber can be present in the separator in an amount of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% relative to the weight of the final separator (the weight of the polyolefin separator or layer containing the rubber and / or latex). In certain embodiments, the rubber can be present in amounts of about 1-6%, about 3-6 wt%, about 3 wt%, and about 6 wt%. The porous membrane can have a weight ratio of filler to polymer and rubber (filler: polymer and rubber) of about 2.6:1.0. The amounts of rubber, filler, oil, and polymer are balanced for operability and desired separator properties such as electrical resistance, basis weight, puncture resistance, flexural stiffness, antioxidant properties, porosity, physical strength, flatness, etc.

[0243] Porous membranes containing polyethylene and a filler (such as silica) manufactured according to the present invention typically have a residual oil content; in some embodiments, this residual oil content is from about 0.5% to about 40% of the total weight of the separator membrane (in some cases, about 10-40% of the total weight of the separator membrane, and in some cases, about 20-40% of the total weight). In certain selected embodiments herein, some to all of the residual oil content in the separator can be replaced by adding more performance-enhancing additives, such as surfactants, such as surfactants with a hydrophilic-lipophilic balance (HLB) of less than 6, or such as nonionic surfactants. For example, performance-enhancing additives such as surfactants, such as nonionic surfactants, can be present in an amount from 0.5% up to all (e.g., up to 20% or 30% or even 40%) of the residual oil content of the total weight of the porous separator membrane, thereby partially or completely replacing the residual oil in the separator membrane.

[0244] Manufacture

[0245] In some embodiments, an exemplary porous membrane can be manufactured by mixing the respective components in an extruder. For example, about 30 wt% filler, about 10 wt% UHMWPE, and about 60% processing oil can be mixed in the extruder. The exemplary porous membrane can be made by the following steps: passing the respective 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 rolls or rollers to form a continuous web. A large amount of the processing oil in the web can be extracted by using a solvent, and then the solvent can be removed by drying. Thereafter, the web can be cut into strips of a predetermined width and wound onto a roll. In addition, various groove patterns can be engraved on the press or calender rolls to impart ribs, grooves, textured areas, protrusions, and / or the like as fully described herein.

[0246] Manufactured with rubber

[0247] In some embodiments, an exemplary porous membrane can be manufactured by mixing the respective constituents in an extruder. For example, about 5 - 15 wt% polymer (such as polyethylene), about 10 - 75 wt% filler (such as silica), about 1 - 50 wt% rubber and / or latex, and about 10 - 85% processing oil can be mixed in the extruder. The exemplary porous membrane can be made by the following steps: passing the respective constituents 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 rolls or rollers to form a continuous web. A large amount of the processing oil in the web can be extracted by using a solvent. Then, the web can be dried and cut into strips of a predetermined width, and thereafter wound onto a roll. In addition, various groove patterns can be engraved on the press or calender rolls to impart ribs, grooves, textured areas, protrusions, and / or the like as fully described herein. The amounts of rubber, filler, oil, and polymer are balanced for operability and desired separator properties (such as electrical resistance, basis weight, puncture resistance, bending stiffness, oxidation resistance, porosity, physical strength, flatness, etc.).

[0248] In addition to being incorporated into the components of the extruder, in certain embodiments the rubber is combined with the porous membrane after extrusion. For example, the rubber can be coated on one or both sides, preferably 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. To improve the wettability of this layer, a wetting agent known for use in lead acid batteries can be added to the slurry. In certain embodiments, the slurry can also contain one or more performance enhancing additives as described herein. After drying, a porous layer and / or film is formed on the separator surface that adheres very well to the porous membrane and only negligibly increases the resistance, if at all. After the rubber is added, it can be further compressed using a mechanical press or calender rolls or rollers. Other possible methods of applying the rubber and / or latex are to apply the rubber and / or latex slurry to one or more surfaces of the separator by dip coating, roll coating, spray coating or curtain coating or any combination thereof. These processes can occur before or after the processing oil is extracted, or before or after the separator is cut into strips.

[0249] A further embodiment of the invention relates to depositing rubber onto the membrane by impregnation and drying.

[0250] Manufactured with performance enhancing additives

[0251] In certain embodiments, performance enhancing additives or reagents (such as surfactants, wetting agents, colorants, antistatic additives, antioxidants and / or the like and any combination thereof) can also be mixed with the other components in the extruder. The porous membrane according to the present disclosure can then be extruded into a sheet or web shape in substantially the same manner as described above and made into a finished product.

[0252] In certain embodiments, as a supplement to or an alternative to being added to the extruder, one or more additives may be applied, for example, to the separator porous membrane when the separator is completed (e.g., after a large amount of processing oil has been extracted and before or after the addition of rubber). According to certain preferred embodiments, an additive or a solution of an additive (such as an aqueous solution) is applied to one or more surfaces of the separator. This variant is particularly suitable for applying non-thermally stable additives and additives that are soluble in the solvent used to extract the processing oil. Particularly suitable solvents for the additives according to the present invention are low molecular weight alcohols such as methanol and ethanol, and mixtures of these alcohols with water. The application can be carried out on the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides. The application can also be carried out simultaneously in a solvent bath during the extraction of the pore former (such as the processing oil). In certain selected embodiments, a portion of the performance enhancing additive (such as a surfactant coating) or the performance enhancing additive (or both) added to the extruder before the manufacture of the separator can bind to the antimony in the battery system and can deactivate it, and / or form a compound with it and / or cause it to fall into the battery sludge and / or prevent its deposition on the negative electrode. A surfactant or additive can also be added to the electrolyte, the glass mat, the battery case, the sticker, the adhesive pad, and / or the like or a combination thereof.

[0253] In certain embodiments, the additive (e.g., a nonionic surfactant, an anionic surfactant, or a mixture thereof) can be present at a density or addition level of at least 0.5 g / m 2 、1.0 g / m 2 、1.5 g / m 2 、2.0 g / m 2 、2.5 g / m 2 、3.0 g / m 2 、3.5 g / m 2 、4.0 g / m 2 、4.5 g / m 2 、5.0 g / m 2 、5.5 g / m 2 、6.0 g / m 2 、6.5 g / m 2 、7.0 g / m 2 、7.5 g / m 2 、8.0 g / m 2 、8.5 g / m 2 、9.0 g / m 2 、9.5 g / m 2 or 10.0 g / m 2 or even up to about 25.0 g / m 2 The additive can be present at 0.5 - 15 g / m 2 、0.5 - 10 g / m 2, 1.0 - 10.0 g / m 2 , 1.5 - 10.0 g / m 2 , 2.0 - 10.0 g / m 2 , 2.5 - 10.0 g / m 2 , 3.0 - 10.0 g / m 2 , 3.5 - 10.0 g / m 2 , 4.0 - 10.0 g / m 2 , 4.5 - 10.0 g / m 2 , 5.0 - 10.0 g / m 2 , 5.5 - 10.0 g / m 2 , 6.0 - 10.0 g / m 2 , 6.5 - 10.0 g / m 2 , 7.0 - 10.0 g / m 2 , 7.5 - 10.0 g / m 2 , 4.5 - 7.5 g / m 2 , 5.0 - 10.5 g / m 2 , 5.0 - 11.0 g / m 2 , 5.0 - 12.0 g / m 2 , 5.0 - 15.0 g / m 2 , 5.0 - 16.0 g / m 2 , 5.0 - 17.0 g / m 2 , 5.0 - 18.0 g / m 2 , 5.0 - 19.0 g / m 2 , 5.0 - 20.0 g / m 2 , 5.0 - 21.0 g / m 2 , 5.0 - 22.0 g / m 2 , 5.0 - 23.0 g / m 2 , 5.0 - 24.0 g / m 2 or a density or additive level between 5.0 - 25.0 g / m 2 exists on the separator.

[0254] Application can also be carried out by immersing the battery separator in an additive or additive solution (solvent bath addition) and removing the solvent if necessary (e.g., by drying). In this way, the application of the additive can be combined, for example, with extraction, which is often applied during membrane production. Other preferred methods are spraying the additive onto the surface, dip - coating, roll - coating, or curtain - coating one or more additives onto the surface of the separator.

[0255] In certain embodiments described herein, a relatively small amount of an ionic, cationic, anionic, or nonionic surfactant is added to the separator of the present invention. In such cases, desirable features may include reduced total organic carbon and / or reduced volatile organic compounds (due to the lower amount of surfactant), and a separator of the present invention may be produced according to such embodiments as desired.

[0256] Combined with fiber mat

[0257] In certain embodiments, an exemplary separator according to the present disclosure may be combined (laminated or otherwise) with one or more other layers, such as a fibrous layer or fibrous mat having enhanced hygroscopicity and / or enhanced wettability or electrolyte retention characteristics. The fibrous mat may be woven, non-woven, flannel, meshed, net, single-layered, multi-layered (where each layer may have the same, similar, or different characteristics as the other layers), made of glass fibers or synthetic fibers, a flannel or fiber made of synthetic fibers or a mixture of glass and synthetic fibers, paper, or any combination thereof. The fibrous mat may be a single piece or individual strips on each side channel.

[0258] In certain embodiments, the fibrous mat (laminated or otherwise) may be used as a carrier for additive materials. Additive materials may include, for example, carbon, BaSO 4 , rubber and / or latex, optional silica, water, and / or one or more performance enhancing additives (such as the various additives described herein) or any combination thereof. By way of example, the additive materials may be provided in the form of a slurry and then coated onto one or more surfaces of the fibrous mat to form a film, or soaked and impregnated into the fibrous mat.

[0259] When there is a fibrous layer, it is preferred that the porous membrane has a larger surface area than the fibrous layer. In this way, when the porous membrane and the fibrous layer are combined, the fibrous layer does not completely cover the porous layer. Preferably, at least two opposite edge regions of the membrane layer remain uncovered to provide edges for heat sealing, which is beneficial for optionally forming bags or envelopes and / or the like. Such a fibrous mat can have a thickness of at least 100 μm, in some embodiments, at least about 200 μm, at least about 250 μm, at least about 300 μm, at least about 400 μm, at least about 500 μm, at least about 600 μm, at least about 700 μm, at least about 800 μm, at least about 900 μm, at least about 1 mm, at least about 2 mm, and so on. The resulting laminated separator can be cut into sheets. In certain embodiments, the fibrous mat is laminated onto the ribbed surface of the porous membrane. In certain embodiments, the improved separator described herein provides advantages in processing and / or assembly for battery manufacturers because it can be supplied in the form of rolls and / or slices. Also as mentioned previously, the improved separator can be a standalone separator sheet or layer without the need to add one or more fibrous mats or the like.

[0260] If the fibrous mat is laminated to the porous membrane, it can be bonded together by means of adhesives, heating, ultrasonic welding, extrusion, and / or the like or any combination thereof. And, the fibrous mat can be a PAM or NAM retention mat.

[0261] Conclusion

[0262] Details of one or more exemplary embodiments, aspects, or objectives are given in the detailed description of the invention and the claims presented below. Other features, objectives, and advantages will be apparent from the detailed description of the invention and the claims presented below. According to one or more selected embodiments, aspects, or objectives, the present disclosure or invention at least solves and in some cases exceeds the above difficulties, problems, or needs.

[0263] According to at least the selected exemplary embodiments, aspects, or objectives, the present invention solves at least the above problems or needs and provides a new or improved separator, a new or improved battery using the new or improved separator, and a new or improved system using the new or improved battery. 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 manufacturing and / or using such new or improved battery separators, battery cells, batteries, and / or systems.

[0264] 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 formulation and rib configuration to reduce or mitigate warping of the electrode plates and / or the effects of electrode plate warping, reduce the occurrence of separator piercing, reduce the occurrence of battery electrode short circuits, and / or the like 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, which may be characterized by at least one or more of the following: anti-plate warping, puncture resistance, oxidation resistance, acid mixing, reduced resistance, improved wettability, improved fillers, optimized porosity, optimized tortuosity, reduced thickness, reduced backsheet thickness, with ribs, negative cross ribs, reduced oil content, increased acid diffusion, enhanced oxidation resistance or improved oxidation stability, optimized porosity, optimized pore tortuosity, improved acid diffusion, and / or the like, 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, which may provide at least one or more of the following: low water loss in the battery and / or cell, reduced resistance in the battery and / or cell, increased acid mixing in the battery and / or cell, reduced acid stratification in the battery and / or cell, improved performance in the battery and / or cell, extended service life in the battery and / or cell, reduced failure rate in the battery and / or cell, and / or the like; and / or combinations thereof.

[0265] According to at least certain exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to a separator, and / or an improved cell and / or battery using the improved separator, and / or an improved system using the improved cell and / or battery (which uses the improved separator), which overcomes at least the foregoing difficulties and / or problems. For example, and by way of example only, the improved cell and / or battery may be characterized by at least one or more of the following: enhanced performance, reduced failure rate, extended service life, reduced occurrence of plate short circuits, reduced occurrence of separator piercing, reduced water loss, reduced floating charge current, improved charge termination current, improved charge acceptability, improved energy throughput, reduced antimony (Sb) poisoning, reduced acid stratification, reduced acid starvation, reduced dendrite formation, reduced internal resistance, improved cold cranking amps (CCA), improved uniformity, improved cycle performance, and / or the like, and / or combinations thereof.

[0266] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention is at least directed to new or improved battery separators, anti-warping separators, puncture-resistant separators, resilient separators, cells, batteries, methods related thereto, systems using them, vehicles using them, methods of manufacturing them, methods of using them, and combinations thereof.

[0267] According to at least certain exemplary embodiments, aspects, or purposes, the present disclosure or invention is directed to new or improved battery separators for use in various batteries and / or applications. Exemplary lists of such batteries and / or applications include: flat batteries, tubular batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, valve-regulated lead-acid (VRLA) batteries, deep-cycle batteries, gel batteries, absorbed glass mat (AGM) batteries, inverter batteries, power harvesting batteries, power storage batteries, batteries for internal combustion engines, auxiliary batteries, starting lighting ignition (SLI) batteries, idle start-stop (ISS) batteries, vehicle batteries, passenger vehicle batteries, automotive batteries, truck batteries, motorcycle batteries, all-terrain vehicle batteries, marine batteries, aircraft batteries, forklift batteries, golf cart or golf car batteries, hybrid electric vehicle (HEV) batteries, mild 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 a partial state of charge (PSoC), and / or the like, and combinations thereof.

[0268] According to at least certain selected exemplary embodiments, aspects, or purposes, an overcurrent system with a battery of the present invention is provided, the battery incorporating the inventive separator described herein. Exemplary systems can be one or more of the following: vehicles, UPSs, auxiliary power systems, power harvester systems, renewable energy harvester systems, wind power harvester systems, solar power harvester systems, backup power systems, inverters, and combinations thereof. Further, exemplary vehicles can be one of the following: automobiles, passenger vehicles, trucks, forklifts, hybrid vehicles, HEVs, mild hybrid vehicles, ISS vehicles, electric vehicles, marine vessels, aircraft, electric rickshaws, electric tricycles, electric bicycles, motorcycles, all-terrain vehicles, golf carts or golf cars, and / or the like, and combinations thereof.

[0269] In a first exemplary embodiment of the present disclosure or invention, an electrode and separator assembly is provided with an electrode plate having a grid and active material thereon. The grid has at least one grid edge. Further, the active material is non-uniformly distributed on the grid. A porous membrane is disposed adjacent to the electrode plate with a first membrane surface. The first membrane surface has a first surface edge and a second surface edge and a plurality of ribs extending from the surface of the membrane; the plurality of ribs extend from the first surface edge to the second surface edge.

[0270] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly is provided with an electrode plate, which can be a positive electrode or a negative electrode, having a grid and an active material unevenly distributed thereon. The grid is provided with a first grid edge and a second grid edge. The porous membrane is arranged adjacent to the electrode plate. The porous membrane has a first side channel adjacent to the first membrane edge and a second side channel adjacent to the second membrane edge, and a central portion located between the first side channel and the second side channel. The porous membrane is provided with a first membrane surface, which has a plurality of main ribs extending out of or into the first membrane surface within the central portion, a first set of secondary ribs arranged in the first side channel, and a second set of secondary ribs arranged in the second side channel.

[0271] In one aspect of the present invention, the first grid edge can be arranged in the first side channel, and the second grid edge can be arranged in the second side channel. The plurality of main ribs can have a uniform height and a uniform distribution. And either or both of the first set of secondary ribs and the second set of secondary ribs are spaced more closely than the plurality of main ribs. The plurality of main ribs, the first set of secondary ribs, and / or the second set of secondary ribs can be arranged longitudinally and substantially parallel to the processing direction of the porous membrane, or arranged transversely and substantially parallel to the transverse processing direction of the porous membrane. Either or both of the first set of secondary ribs and the second set of secondary ribs can be substantially parallel, orthogonal, or angled with respect to the plurality of main ribs. The porous membrane can have a second membrane surface, on which there is a third set of ribs.

[0272] In another aspect of the present invention, the grid can be any one of a stamped grid, a cast grid, or an expanded metal grid. Further, the grid may undergo warping. The grid can have a first grid surface and a second grid surface, and wherein, compared with the second grid surface, the active material can be more heavily distributed on the first grid surface. Further, the active material can be unevenly distributed on the grid surface.

[0273] In yet another aspect, any one of the plurality of main ribs, the first set of secondary ribs, the second set of secondary ribs, and / or the third set of ribs can be one or more of the following: an uninterrupted rib, a discrete discontinuous rib, a continuous rib, a discontinuous rib, a discontinuous peak, a discontinuous protrusion, an angled rib, a diagonal rib, a linear rib, a rib extending substantially longitudinally in the processing direction of the porous membrane, a rib extending substantially transversely in the transverse processing direction of the porous membrane, a rib extending transversely across the transverse processing direction of the separator, a discrete tooth, a toothed rib, a serrated protrusion, a serrated rib, a stack-like protrusion, a stack-like rib, a curved rib, a continuous sinusoidal rib, a discontinuous sinusoidal rib, an S-shaped rib, a continuous zigzag serrated rib, a discontinuous discontinuous zigzag serrated rib, a groove, a trough, a textured area, a protrusion, a depression, a pillar, a micro-pillar, porous, non-porous, cross ribs, micro-ribs, cross micro-ribs, and combinations thereof.

[0274] In certain embodiments, the porous membrane can be one of the following: an envelope, a hybrid envelope, a sleeve separator, a bag separator, and a wrap separator. The porous membrane can have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof. The porous membrane can also be a slice.

[0275] In another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly is provided with electrode plates, which can be positive or negative electrodes, having grids and active materials unevenly distributed thereon. The porous membrane can be provided with a first membrane surface having a main rib array located thereon and extending from a first membrane edge to a second membrane edge; wherein, the main rib array has a uniform height.

[0276] Another aspect of the present invention or disclosure provides a grid having a first grid surface and a second grid surface, with the active material being more heavily distributed on the first grid surface compared to the second grid surface. As an alternative, or additionally, the active material can be unevenly distributed on the grid surface. The grid can be one of the following: a stamped grid, a cast grid, and an expanded metal grid. Additionally, the grid may be subject to warping. Either the first membrane surface or the second membrane surface can be adjacent to the electrode plate.

[0277] In another aspect of the present invention, the main rib array can be arranged longitudinally and substantially parallel to the processing direction of the porous membrane, and can be evenly or unevenly laterally spaced across the entire processing direction of the porous membrane. The porous membrane is provided with a second surface, and a second set of ribs can extend from the second surface.

[0278] In another aspect of the present invention or disclosure, one or both of the main rib array and / or the second set of ribs can be one or more of the following: an uninterrupted rib, a discrete discontinuous rib, a continuous rib, a discontinuous rib, a discontinuous peak, a discontinuous protrusion, an angled rib, a diagonal rib, a linear rib, a rib extending substantially longitudinally in the processing direction of the porous membrane, a rib extending substantially laterally in the transverse direction of the porous membrane, a rib extending transversely across the transverse direction of the separator, discrete teeth, toothed ribs, serrated protrusions, serrated ribs, stack-like protrusions, stack-like ribs, curved ribs, continuous sinusoidal ribs, discontinuous sinusoidal ribs, S-shaped ribs, continuous zigzag serrated ribs, discontinuous discontinuous zigzag serrated ribs, grooves, channels, textured areas, protrusions, depressions, columns, micro-columns, porous, non-porous, cross ribs, micro-ribs, cross micro-ribs, and combinations thereof.

[0279] In an exemplary aspect, the porous membrane can be one of the following: an envelope separator, a hybrid envelope separator, a sleeve separator, a bag separator, a wrapped separator, a sliced separator, a vane separator; wherein, the envelope, hybrid envelope, sleeve separator, bag separator, and wrapped separator can have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof.

[0280] In yet another exemplary embodiment of the present invention or disclosure, the electrode and separator assembly can be provided with an electrode plate provided with a grid and an active material. The grid can have a first grid edge and a second grid edge, and the active material can be unevenly distributed on the grid. The porous membrane can further be provided with a first membrane surface having a support structure that supports the first grid edge and the second grid edge. The first grid edge can have at least a first grid corner, and the second grid edge can have at least a second grid corner. The support structure can have a first set of ribs having a uniform height.

[0281] The grid can have a first grid surface and a second grid surface, wherein the active material can be more heavily distributed on the first grid surface compared to the second grid surface. As an alternative, or additionally, the active material can be unevenly distributed on the grid surface. The grid can be one of the following: a stamped grid, a cast grid, and an expanded metal grid. The electrode plate may be subject to warping.

[0282] In a particular exemplary aspect, the first set of ribs can be uniformly laterally spaced from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane. The first set of ribs can also be uniformly or non-uniformly laterally spaced from the first membrane edge of the porous membrane to the second membrane edge of the porous membrane.

[0283] In other exemplary aspects of the present disclosure, compared to the rib spacing in the central portion of the porous membrane, the first set of ribs can be more closely spaced in a first membrane region adjacent to the first membrane edge and in a second membrane region adjacent to the second membrane edge.

[0284] In yet another exemplary aspect of the present disclosure, the first set of ribs can be uniformly or non-uniformly laterally spaced from the first grid edge to the second grid edge. Additionally, compared to the rib spacing in the central portion of the grid, the first set of ribs can be more closely spaced in a first region adjacent to the first grid edge and in a second region adjacent to the second grid edge.

[0285] In yet another aspect of the present disclosure, the support structure can have a fiber mat that can extend from the first grid edge to the second grid edge. The support structure can have a first fiber mat adjacent to the first grid edge and a second fiber mat adjacent to the second grid edge.

[0286] In another exemplary aspect, the porous membrane can be one of the following: an envelope separator, a hybrid envelope separator, a sleeve separator, a bag separator, a wrap separator, a slice separator, and a vane separator; wherein, the envelope, hybrid envelope, sleeve separator, bag separator, and wrap separator can have at least one sealed edge formed by crimping, welding, ultrasonic welding, thermal welding, adhesives, and combinations thereof.

[0287] In yet another exemplary embodiment of the present disclosure, a lead-acid battery can be provided with a separator as fully described herein. The lead-acid battery can operate in one of the following states: in motion, stationary, in a standby power application, in a deep cycle application, in a cycling application, in a partially charged state, and combinations thereof.

[0288] Exemplary batteries can be one of the following: flat batteries, flooded lead-acid batteries, enhanced flooded lead-acid (EFB) batteries, valve-regulated lead-acid (VRLA) batteries, deep cycle batteries, gel batteries, absorbed glass mat (AGM) batteries, tubular batteries, inverter batteries, vehicle batteries, starting lighting ignition (SLI) vehicle batteries, idle start-stop (ISS) vehicle batteries, automotive batteries, truck batteries, marine batteries, motorcycle batteries, all-terrain vehicle batteries, forklift batteries, golf cart batteries, hybrid electric vehicle batteries, electric vehicle batteries, electric rickshaw batteries, electric tricycle batteries, and electric bicycle batteries.

[0289] In yet another exemplary embodiment, a system can be provided with a lead-acid battery as described herein. The system can be provided with a vehicle, where the vehicle can be one of the following: 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 marine vessel, an electric rickshaw, an electric tricycle, and an electric bicycle. Further, the system can operate in one of the following states: in motion, stationary, in a standby power application, in a deep cycle application, in a cycling application, in a partially charged state, and combinations thereof. The system can 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.

[0290] In another exemplary embodiment, a method for reducing grid warping in an electrode and separator assembly can be provided. The method can provide an electrode plate having a grid prone to warping; a porous membrane adjacent to the grid; and a support structure located between the porous membrane and the grid. The active material can be applied unevenly to the grid. The grid can have an outer edge. The support structure can overlap at least a portion of the outer edge of the grid. The support structure can be provided as a set of ribs extending from the porous membrane and having a uniform height. The set of ribs can be longitudinally arranged in the processing direction of the porous membrane, and the set of ribs can be evenly spaced in the transverse dimension from a first edge of the outer edge to a second edge of the outer edge across the processing direction. As an alternative, or additionally, the support structure can have or be a polygonal spacer. As an alternative, or additionally, the support structure can have or be a fiber mat. As an alternative, or additionally, the support structure can have or be a first fiber mat and a second fiber mat, wherein the first fiber mat is arranged to at least partially overlap the first edge of the outer edge, and the second fiber mat is arranged to at least partially overlap the second edge of the outer edge. The method can further provide subjecting the electrode and separator assembly to high temperature and / or thermal cycling.

[0291] According to at least selected exemplary embodiments, aspects, or purposes, the present disclosure or invention provides a separator, its assembly, and physical properties and characteristics that are synergistically combined to unexpectedly solve previously unmet needs 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, which unexpectedly solves previously unmet needs 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, which unexpectedly solves previously unmet needs in the lead-acid battery industry with an improved system (which uses the lead-acid battery of the present invention, which uses the separator of the present invention described herein).

[0292] According to at least selected exemplary embodiments, aspects, or purposes, the present invention solves, meets, and / or overcomes at least some of the difficulties, needs, and / or problems that have not been solved, met, and / or addressed by the current prior art to date. According to at least a specific purpose, the present invention provides an improved separator, an improved battery cell or battery using the improved separator, and / or an improved system using the improved separator, battery cell, or battery, which overcomes at least the specific foregoing difficulties, problems, or needs.

[0293] According to at least selected exemplary embodiments, aspects, or objectives, the present disclosure or invention can address at least the above difficulties, problems, or needs, and / or can provide a new or improved separator, a warpage-resistant separator, and / or a lead-acid battery separator, a new or improved battery cell or battery using the new or improved separator, and / or a new or improved system using the new or improved separator, battery cell, or battery. According to at least specific exemplary embodiments, aspects, or objectives, the present disclosure or invention is directed to a new or improved battery separator, battery cell, battery, system, and / or a method of manufacturing and / or using such new or improved battery separator, battery cell, battery, and / or system.

[0294] Disclosed herein are exemplary embodiments related to an improved electrode plate and separator assembly (400) for a lead-acid battery, an improved lead-acid battery cell or battery including the improved assembly, a system or vehicle including the improved assembly (400) and / or battery (100), and related methods. The electrode plates (200, 201) may have grids (202) of a stamping, casting, or expanded metal manufacturing process. The grids (202) may have unevenly coated active materials (203). The separator (300) preferably provides a support structure for resisting or alleviating any plate warpage or plate skew.

[0295] According to at least selected embodiments, the present disclosure or invention is directed to separators, particularly separators for lead-acid batteries, which are capable of reducing or alleviating water loss in the battery, reducing antimony (Sb) poisoning, alleviating warping, bending or cupping of the electrode plate grids, reducing or alleviating acid deficiency, reducing or alleviating acid stratification, reducing or slowing dendrite growth, alleviating the effects of oxidation, reducing water loss, increasing wettability, improving acid diffusion, enhancing uniformity, and having a reduced resistance, capable of increasing the cold start current and / or the like and combinations thereof. Additionally, disclosed herein are methods, systems, and battery separators that are used at least in enhanced flooded lead-acid batteries to extend battery life, reduce battery water loss, reduce battery antimony (Sb) poisoning, reduce or alleviate warping, bending or cupping of the electrode plate grids, reduce or alleviate acid deficiency, reduce or alleviate acid stratification, reduce or alleviate dendrite growth, reduce the effects of oxidation, reduce internal resistance, increase wettability, improve acid diffusion, improve cold start current, enhance uniformity and / or the like and any combinations thereof. According to at least specific embodiments, the present disclosure or invention is directed to an improved separator for an enhanced flooded lead-acid battery, wherein the separator comprises an improved formulation for reducing battery water loss and reducing antimony (Sb) poisoning, improved resistance to separator grid warping, increased separator elasticity, and combinations thereof. According to at least particular embodiments, the present disclosure or invention is directed to an improved separator for an enhanced flooded lead-acid battery, wherein the separator comprises an improved formulation that includes a crosslinking component, a performance-enhancing additive or coating, increased antioxidant properties, amorphous silica, silica with a higher oil absorption rate, silica with a higher silanol group, silica with an OH:Si ratio of 21:100 to 35:100, a polyolefin microporous membrane (which contains particulate fillers accounting for 40% or more of the weight of the membrane and polymer (such as ultra-high molecular weight polyethylene (UHMWPE))), a reduced sheet thickness, a reduced thickness, a reduced oil content, increased wettability, improved acid diffusion and / or the like, and any combinations thereof.

[0296] Some of the embodiments described herein are further illustrated in the following non-limiting examples.

[0297] Example 1

[0298] Battery testing in motion

[0299] The driving modes of automobiles, forklifts, and golf carts were determined by installing a dynamometer on the vehicle to measure the forces generated in typical driving modes, and the results are shown in Figure 17 . As Figure 17As shown, a motion platform has been developed that is capable of testing multiple batteries of different sizes simultaneously and has the ability to vary the g-force. The platform is equipped with a dynamometer to confirm that the actual g-force matches those observed in the field and can also interact with a cycler to limit movement during charging or discharging.

[0300] Example 2

[0301] NAM swelling and acid deficiency

[0302] Comparison Figure 16 the performance of the computer-optimized hybrid separator (RipTide M) in Figure 18 and the non-stop rib profile separator in th Do not overcharge the battery to minimize venting. Compared to a battery with a standard non-stop rib profile, the battery with Rip Tide M shows a higher voltage. This voltage difference indicates that the acid is being mixed or not allowed to fully stratify.

[0303] However, the battery with RipTide M shows a performance degradation. Disassembly analysis of the battery, as Figure 18 shown, reveals excessive swelling of the NAM in the reverse image of the separator profile. In other words, the NAM swells into any area where there are no ribs to hold it in place. From this observation, it is certain that as the battery cycles, the NAM actually swells enough to block channels that are typically less than 1.0 mm thick and becomes acid-deficient due to the inability to passively mix the acid. Therefore, to extend the service life of PSoC batteries, it is desirable to mix the acid and prevent NAM swelling simultaneously.

[0304] Example 3

[0305] NAM swelling and increased separator rib quantity

[0306] Regarding the NAM swelling shown in Example 2, the deeper the battery discharges, the more lead is converted into the larger-volume lead sulfate. If the active material is not constrained, it will fill the space between the separator ribs. To convert the lead sulfate back to lead, the swollen active material needs to have electronic conductivity to the current-carrying grid. The separators used in traditional SLI batteries are designed assuming that the battery is not cycled regularly. Different from the separators used in moving power batteries, SLI separators have a small number of ribs, usually around 11. However, Example 2 demonstrates that when SLI separators are used in cycling EFB applications, there will be a large area of unsupported active material that swells, becomes inert, and prevents passive acid mixing. A more compressive separator is needed.

[0307] As Figure 19As shown, by significantly increasing the number of ribs, for example from 11 to 35, the area of unsupported active material is greatly reduced. When the individual areas of the swollen active material decrease in size, the likelihood of the swollen active material remaining in electrical contact with the grid is high, and the likelihood of the swollen active material ultimately being reduced from lead sulfate to lead during recharging is increased.

[0308] Use Figure 16 The "computational fluid dynamics" model used in Figure 20 is used to explore the passive acid mixing ability of separators with a larger number of ribs. As

[0309] As Figure 20 shown, the mixing ability of an uninterrupted rib configuration and a compression-resistant serrated rib configuration with 35 ribs is compared. As shown, the horizontal channels of the serrated separator with 35 ribs can perform acid mixing. This separator design that combines acid mixing and compression resistance is called Rip Tide C.

[0310] As

[0311] shown, on the moving platform of Example 1, batteries manufactured with Rip Tide C and standard SLI separators are tested in a partially charged state without overcharging. The battery with the SLI separator quickly runs out of power. However, due to the restricted swelling of the active material and the rib serrations allowing acid mixing, the battery with the Rip Tide C separator shows a significant improvement in service life.

[0310] By providing a solution to NAM swelling in this PSoC test, the battery service life is significantly extended. Along with a higher voltage, this indicates that the acid is being mixed. Thus, when an automotive battery transitions from fully charged to PSoC operation, the separator design can be adjusted to achieve a longer service life.

[0311] Example 4

[0312] Discharge level and NAM swelling

[0313] As Figure 21 shown, the choice of separator design is matched to the depth of discharge the battery will experience. The deeper the battery discharges, the more NAM swells, and more compression is required to ensure proper battery recovery. If the discharge is shallow, such as less than 5% used in the SBA test, the NAM swelling is negligible, Figure 16 and the Rip Tide M or optimized mixing configuration in

[0314] Example 5

[0315] Conventional SLI separator failure under PSoC

[0316] Based on the findings described in Examples 2 - 4 regarding extending the service life in PSoC operation to improve charge acceptance, it can be predicted that conventional SLI rib spacing will allow unsupported active material to continue to swell, resulting in poor charge acceptance. As Figure 22 shown, the prediction was verified by scanning electron microscope (SEM) images of the active material in a battery with a separator having conventional SLI rib spacing, by showing a high concentration of lead sulfate.

[0317] Also as Figure 22 shown, if a typical SLI separator with 11 ribs is placed on the grid, 1 / 3 of the agglomerates will not immediately contact the ribs to hold them in place. When the battery operates under PSoC, the unsupported active material will expand and eventually lose contact with the grid and then fall off when operating under PSoC. Therefore, using an SLI separator results in poor charge acceptance.

[0318] Example 6

[0319] PSoC cycling of battery with compressive separator

[0320] Figure 23 Shows the effect of PSoC cycling on the swelling of the active material in a battery with a compression-resistant separator, Rip Tide M. SEM of the active material shows that the NAM is in a very healthy state. When viewing the same grid, each active material agglomerate has support from multiple ribs to hold it in place. As shown, after disassembling the battery after operation under PSoC, all agglomerates are intact and the NAM has not swollen excessively. Therefore, when the NAM is constrained by a compression-resistant separator and remains in contact with the grid, charge acceptance will be improved.

[0321] Figure 24 Shows the effect of PSoC cycling on the swelling of the active material in a battery with a compression-resistant separator, Rip Tide C. At 80% state of charge, by changing to this separator configuration, the DCA increased by 30%. Therefore, compared to a battery with a conventional SLI separator, this compression-resistant separator constrains the NAM and minimizes the pockets of lead sulfate swelling, thus improving the DCA.

[0322] Example 7

[0323] Nucleating additive

[0324] Contrary to conventional methods of mixing a small amount of nucleating additive, such as carbon, into the active electrode material, in some embodiments described herein, the nucleating additive is placed on the surface of the negative electrode such that when lead sulfate forms, it is in intimate contact with the lead sulfate. In some cases, the application method described herein is to coat the side of the separator that is in direct contact with the negative electrode with carbon, as Figure 25 and 26 shown.

[0325] Figure 27 Shows a thin layer of carbon deposited on the separator. In this case, the thin coating is approximately 10 microns thick and approximately 11 grams of carbon are added to one square meter of separator. As seen from the SEM, this layer of carbon is actually porous and only negligibly increases the ER. When carbon is added through the separator, approximately 15 grams of carbon are introduced into the battery, which is far less than the amount of carbon used in conventional methods of adding carbon to the NAM.

[0326] This method has many advantages. Since less carbon is introduced into the system, less water is lost, and by removing the carbon from the NAM, the hassle of absorbing the expander and the resulting power loss is avoided. The main question now is to determine whether such a carbon-coated separator actually improves charge acceptance.

[0327] As Figure 28 shown, coating the carbon on the SLI separator shows a negligible improvement in DCA (Dynamic Charge Acceptance). However, when the same coating is applied to the compression-resistant separator, the DCA increases. When compared to the industry standard of uncoated SLI separators, the battery with a compression-resistant separator with a carbon coating (Rip Tide C in this case) can increase the DCA by 85%.

[0328] According to at least certain embodiments, aspects, or purposes, the present disclosure or invention is directed to or may provide new or improved separators for various lead-acid batteries and / or systems. Additionally, the exemplary embodiments disclosed herein are directed to new or improved battery separators, separator configurations, separator and electrode assemblies including the same, battery cells including the same, batteries including the same, systems including the same, and / or methods of making and / or using the same, and / or the like, and / or combinations thereof. For example, disclosed herein are exemplary embodiments of an improved electrode plate and separator assembly (400) for a lead-acid battery, an improved lead-acid battery cell or battery including the improved assembly, a system or vehicle including the improved assembly (400) and / or battery (100), and related methods. The electrode plates (200, 201) may have grids (202) formed by stamping, casting, or expanded metal manufacturing processes. The grids (202) may have non-uniform application of active material (203). The separator (300) provides a support structure for resisting or alleviating any plate warping or plate deflection.

[0329] According to at least selected exemplary embodiments, aspects, or purposes, the present disclosure or invention is at least directed to new or improved battery separators characterized by one or more of the following: anti-plate warping separators, puncture-resistant separators, resilient separators, battery cells, batteries, related methods of using or including the same, related systems of using or including the same, related vehicles of using or including the same, methods of making the same, and / or the like, and / or combinations thereof. According to at least certain exemplary embodiments, aspects, or purposes, 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 the following: enhanced performance, reduced failure rate, extended service life, reduced occurrence of plate short circuits, reduced occurrence of separator punctures, and / or the like, and / or combinations thereof.

[0330] The present disclosure or invention is directed to new or improved separators for various lead-acid batteries and / or systems. Additionally, the exemplary embodiments disclosed herein are directed to new or improved battery separators, separator configurations, separator and electrode assemblies including the same, battery cells including the same, batteries including the same, systems including the same, and / or methods of making and / or using the same, and / or the like, and / or combinations thereof. For example, disclosed herein are exemplary embodiments of an improved electrode plate and separator assembly (400) for a lead-acid battery, an improved lead-acid battery cell or battery including the improved assembly, a system or vehicle including the improved assembly (400) and / or battery (100), and related methods. The electrode plates (200, 201) may have grids (202) made by stamping, casting, or expanded metal manufacturing processes. The grids (202) may have non-uniform application of active material (203). The separator (300) provides a support structure for resisting or alleviating any plate warping or plate deflection.

[0331] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims, and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various variations of the compositions and methods are also intended to fall within the scope of the appended claims, in addition to those shown and described herein. Furthermore, although only specific representative compositions and method steps disclosed herein are specifically described, other combinations of composition and method steps are also intended to fall within the scope of the appended claims, even if not specifically recited. Thus, combinations of steps, elements, components, or ingredients may be explicitly or less explicitly mentioned herein, but other combinations of steps, elements, components, and ingredients are included even if not explicitly stated. As used herein, the terms "comprising" and variations thereof are used synonymously with the term "including" and variations thereof, and are open-ended, non-limiting terms. Although the terms "comprising" and "including" have been used to describe various embodiments herein, the terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the invention, and are also disclosed. Except as otherwise indicated in the examples or elsewhere, all numbers expressing quantities of ingredients, reaction conditions, etc. used in the specification and claims should be understood to be modified in all instances by the term "about," at least to the extent that the application of the doctrine of equivalents is not to be limited to the scope of the claims, and should be interpreted in accordance with the number of significant digits and the ordinary rounding method.

[0332] Without departing from the spirit and essential attributes of the present invention, the present invention may be implemented in other forms. Therefore, when indicating the scope of the present invention, reference should be made to the appended claims rather than the foregoing description. What is disclosed are components that can be used to implement the disclosed methods and systems. These and other components are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed, although specific references to each individual and collective combination and arrangement may not be explicitly disclosed, each and every one of them is specifically contemplated and described herein for all methods and systems. This applies to all aspects of the present application, including but not limited to the steps in the disclosed methods. Thus, if multiple additional steps can be performed, it should be understood that each of these additional steps can be performed in conjunction with any specific implementation or combination of implementations of the disclosed method.

[0333] The foregoing written description of the structures and methods is given for purposes of illustration only. The examples are used to disclose exemplary embodiments, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system and performing any associated method. The examples are not intended to be exhaustive or to limit the present invention to the precise steps and / or forms disclosed, and many modifications and variations are possible in light of the above teachings. The features described herein can be combined in any combination. The steps of the methods described herein can be performed in any physically possible order. The patentable scope of the present invention is defined by the appended claims and may include other embodiments that occur to those skilled in the art. If such other embodiments have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims, then such other embodiments are intended to be within the scope of the claims.

[0334] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended to illustrate several aspects of the claims. Any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various variations of the compositions and methods, in addition to those shown and described herein, are also intended to fall within the scope of the appended claims. Moreover, although only specific representative compositions and method steps disclosed herein are specifically described, other combinations of composition and method steps are also intended to fall within the scope of the appended claims even if not specifically recited. Thus, combinations of steps, elements, components, or ingredients may be mentioned explicitly or less explicitly herein, but other combinations of steps, elements, components, and ingredients are included even if not explicitly stated.

[0335] As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When expressing such a range, another embodiment includes from one particular value and / or to another particular value. Similarly, when values are expressed as approximations by use of the antecedent "about", it will be understood that the particular value forms another embodiment. It should also be understood that each end point of a range is significant both in relation to the other end point and independently of the other end point. "Optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0336] Throughout the specification and claims of this specification, the word "comprising" and variations of the word, such as the participle form "comprising" and the singular form "comprises", mean "including but not limited to", and are not intended to exclude, for example, other additives, components, integers or steps. The terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the invention and 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 not restrictive but is for explanatory or illustrative purposes. Additionally, unless otherwise indicated by dimensions in the text or the drawings, any drawings should not be construed as being drawn to scale.

[0337] Unless otherwise stated, all numbers expressing geometric shapes, dimensions, etc. used in the specification and claims should at least be understood as not being attempts to limit the application of the doctrine of equivalents to the scope of the claims, and should be interpreted in accordance with the number of significant digits and the normal rounding-off method.

[0338] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention pertains. Publications and the materials cited therein are specifically incorporated herein by reference.

[0339] In addition, the invention disclosed herein by way of example may be practiced appropriately in the absence of any element not specifically disclosed herein.

Claims

1. A component composed of an electrode plate and a pure porous membrane separator, wherein, the electrode plate includes a grid which is a conductor and has openings between the conductors; the grid includes an active material applied thereon, and the active material forms agglomerates within the openings; the separator has a first surface facing and directly contacting the negative electrode plate, the first surface has multiple columns and / or rows of first ribs, the first ribs have multiple discrete protrusions, carbon is coated on the first surface directly contacting the negative electrode plate, and the thickness of the carbon coating is 10 micrometers; the discrete protrusions support the conductor, block at least a part of the openings, prevent the negative electrode active material from falling off, and prevent the agglomerates from being pushed out of the openings.

2. The component according to claim 1, wherein, there is a glass pad or sticker on one or both sides of the porous membrane; or, there is no glass pad or sticker on one or both sides of the porous membrane.

3. The component according to claim 1, wherein, the multiple columns of first ribs are longitudinally arranged in the processing direction and are laterally spaced apart across the processing direction; or, the multiple columns of first ribs are laterally arranged across the processing direction and are longitudinally spaced apart in the processing direction.

4. The component according to claim 1, wherein, the multiple columns of first ribs are uninterrupted ribs or discrete intermittent ribs; the multiple columns of first ribs are continuous ribs or discontinuous ribs; the multiple columns of first ribs are discontinuous peaks or discontinuous protrusions; the multiple columns of first ribs are angled ribs; the multiple columns of first ribs are acid-mixed ribs; the multiple columns of first ribs are diagonal ribs; the multiple columns of first ribs are linear ribs, including ribs longitudinally extending in the processing direction of the porous membrane, ribs laterally extending across the processing direction of the porous membrane, ribs transversely cutting across the processing direction of the separator; the multiple columns of first ribs are discrete teeth or toothed ribs; the multiple columns of first ribs are serrated protrusions, serrated ribs, stack-like protrusions, or stack-like ribs; the multiple columns of first ribs are curved ribs; the multiple columns of first ribs are continuous sinusoidal ribs or discontinuous sinusoidal ribs; the multiple columns of first ribs are S-shaped ribs; the multiple columns of first ribs are continuous zigzag serrated ribs or intermittent discontinuous zigzag serrated ribs; the multiple columns of first ribs are grooves or trenches; the multiple columns of first ribs are textured areas or protrusions; the multiple columns of first ribs are depressions or columns; the multiple columns of first ribs are micro-columns; the multiple columns of first ribs are porous or non-porous; the multiple columns of first ribs are cross ribs; the multiple columns of first ribs are micro-ribs; or, the multiple columns of first ribs are cross micro-ribs.

5. The component according to claim 1, wherein, The porous membrane includes a second surface facing away from the electrode plate, which has multiple columns of second ribs; preferably, the multiple columns of second ribs are uninterrupted ribs or discrete and discontinuous ribs; the multiple columns of second ribs are continuous ribs or discontinuous ribs; the multiple columns of second ribs are discontinuous peaks or discontinuous protrusions; the multiple columns of second ribs are angled ribs; the multiple columns of second ribs are acid-mixed ribs; the multiple columns of second ribs are diagonal ribs; the multiple columns of second ribs are linear ribs, including ribs longitudinally extending in the processing direction of the porous membrane, ribs laterally extending in the transverse direction across the processing direction of the porous membrane, and ribs transversely cutting and extending in the transverse direction of the separator; the multiple columns of second ribs are discrete teeth or tooth-shaped ribs; the multiple columns of second ribs are serrated protrusions, serrated ribs, stack-shaped protrusions, or stack-shaped ribs; the multiple columns of second ribs are curved ribs; the multiple columns of second ribs are continuous sinusoidal ribs or discontinuous sinusoidal ribs; the multiple columns of second ribs are S-shaped ribs; the multiple columns of second ribs are continuous zigzag serrated ribs or discontinuous and discontinuous zigzag serrated ribs; the multiple columns of second ribs are grooves or trenches; the multiple columns of second ribs are textured areas or protrusions; the multiple columns of second ribs are depressions or columns; the multiple columns of second ribs are micro-columns; the multiple columns of second ribs are porous or non-porous; the multiple columns of second ribs are cross ribs; the multiple columns of second ribs are micro ribs; or, the multiple columns of second ribs are cross micro ribs.

6. The assembly of an electrode and a separator according to claim 1, wherein, the porous membrane is one of the following: an envelope separator, a hybrid envelope separator, a sleeve separator, a bag separator, a wrapped separator, a sliced separator, and a vane separator.

7. An assembly composed of an electrode plate and a pure porous membrane separator, wherein, the electrode plate includes a conductor grid, and there are openings between the conductor grid structures; agglomerated active materials are arranged in the openings; the separator has a first surface facing and directly contacting the electrode plate, the first surface has multiple columns and / or multiple rows of first ribs, there is a first interval between the first ribs, the first ribs have multiple discrete teeth, and there is a second interval between each discrete tooth; the first surface of the porous membrane is covered or coated with a carbon coating; the second interval is less than or equal to the first interval, or, the first interval is a multiple of the second interval, the discrete teeth support the conductor grid and at least block part of the openings to prevent the agglomerates from being pushed out of the openings.

8. A lead-acid battery separator (300), wherein, the separator has a first surface facing and directly contacting the electrode plate, the first surface has multiple columns and / or multiple rows of first ribs, the first ribs have multiple discrete protrusions, and carbon is coated on the first surface directly contacting the negative electrode plate; the separator further includes non-woven materials, glass mats, fiber mats, AGM, active material holding mats, and / or sticker papers.

9. An electrode plate (200, 201) of a lead-acid battery, wherein, It has a conductor grid (202) obtained by stamping, casting or expanded metal; the grid (202) contains uneven active material (203); at least a part of the active material (203) faces the support structure of the battery separator (300).

10. A method for improving the dynamic charge acceptance ability of a battery, wherein, remove carbon in the NAM; and apply a small amount of carbon on the compression-resistant separator.

11. A lead-acid battery, comprising the component according to claim 1 or 7.

12. An electric vehicle, comprising the lead-acid battery according to claim 11.

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