Improved performance lead-acid battery separator, battery and vehicle having the separator, and related methods

Abstract

To provide: battery separators for enhanced flooded lead-acid batteries, such as enhanced flooded start / stop batteries, that do not undergo stratification while in use and / or that exhibit reduced or significantly reduced levels of stratification while in use; and lead-acid batteries, vehicles, and related methods.SOLUTION: A battery separator for enhancing acid mixing in a flooded lead-acid battery comprises: a porous backweb and a plurality of broken ribs extending from at least one side of the backweb; and at least a portion of the plurality of broken ribs being defined by an angular orientation to enhance acid mixing especially during battery movement with the separator positioned parallel to start and stop motion of the battery.SELECTED DRAWING: Figure 26D

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority and interest to U.S. Provisional Patent Application No. 62 / 238373 filed on October 7, 2015, PCT Patent Application No. PCT / US2016 / 012805 filed on January 11, 2016 (claiming priority to U.S. Provisional Patent Application No. 62 / 238373 filed on October 7, 2015), and 62 / 385347 filed on September 9, 2016. The entire contents of each of these are incorporated herein by reference in full.

[0002] In at least selected embodiments, the Disclosure covers improved lead-acid batteries, improved systems including lead-acid batteries, and / or battery separators, improved vehicles including such systems, methods of manufacture or use, or combinations thereof, such as submersible lead-acid batteries. In at least specific embodiments, the Disclosure or Invention covers improved submersible lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacture, inspection or use, or combinations thereof, such improved submersible lead-acid batteries. In addition, the Specification also discloses methods, systems, batteries, and / or battery separators for reducing stratification in submersible lead-acid batteries and in such batteries operating under partial-state charging, thereby extending battery life and performance. [Background technology]

[0003] To reduce fuel consumption and exhaust emissions, automakers have implemented varying degrees of electric hybridization. One form of hybrid electric vehicle (HEV) is sometimes called a "micro HEV" or "micro hybrid." In such micro HEVs or similar vehicles, the vehicle may have an idle start / stop (ISS) function, in which the engine may stop at various points during idle start / stop and / or regenerative braking. This improves the vehicle's fuel efficiency but also increases the burden on the battery, which must power auxiliary devices (such as air conditioning and media players) while the vehicle is stopped.

[0004] Conventional vehicles (such as cars without start / stop functionality) may use conventional submersible lead-acid batteries, such as start-up ignition (SLI) lead-acid batteries. Since the engine never stops while in use, power is drawn from the battery only when the engine is cranked. At such times, the battery is typically overcharged, not just partially charged. For example, such conventional submersible lead-acid batteries may be charged to more than 95%, more than 96%, more than 97%, more than 98%, more than 99%, or even more than 100%, often being overcharged. In overcharging, gas bubbles (e.g., hydrogen gas bubbles) are generated within the conventional lead-acid battery, and these circulating gas bubbles mix the liquid electrolyte (acid) within the battery.

[0005] On the other hand, start / stop vehicles continuously draw power from the battery and are therefore always in a partially charged state. In a partially charged state, gas bubbles are not generated, mixing within the electrolyte is greatly reduced, and stratification occurs within the battery. Thus, stratification is a problem in start / stop submersible lead-acid batteries and various enhanced submersible batteries, but it has not been a problem at all in more conventional and traditional submersible lead-acid batteries that operate in an overcharged or fully (or nearly fully) charged state.

[0006] Stratification is a term relating to the process in which concentrated sulfuric acid is concentrated at the bottom of the battery, leading to a correspondingly higher water concentration at the top. Stratification is undesirable in submersible lead-acid batteries, such as reinforced submersible lead-acid batteries or start / stop submersible lead-acid batteries. A decrease in acid levels at the top of the electrodes can impair uniformity and charge acceptance within the battery system, potentially increasing the variation in internal resistance from top to bottom along the height of the battery. An increase in acid levels at the bottom of the battery can interfere with the battery management system, potentially causing an artificial increase in battery voltage and sending unintended / false health signals to the battery management system. In general, stratification causes high resistance along the battery's structure, which may lead to electrode problems and / or a shortened battery lifespan. If start / stop batteries and / or other enhanced submersible lead-acid batteries are to become increasingly prevalent with hybrid and fully electric vehicles, and are expected to increase vehicle fuel efficiency and reduce CO2 emissions, then solutions for reducing stratification and / or improving acid mixing are greatly needed.

[0007] In some cases, stratification can be avoided by using valve-regulated lead-acid (VRLA) technology, in which the acid is immobilized by either a gel electrolyte and / or a glass mat absorption (AGM) battery separator system. In contrast to the free fluid electrolyte in immersion lead-acid batteries, in VRLA-AGM batteries, the electrolyte is absorbed by fibrous materials such as fibers or glass fiber mats, polymer fiber mats, or gel electrolytes. However, the manufacturing cost of VRLA-AGM battery systems is significantly higher than that of immersion battery systems. VRLA-AGM technology may, in some cases, be more sensitive to overcharging, dry out at high temperatures, experience a gradual decrease in capacity, and have lower specific energy. Similarly, in some cases, gel VRLA technology may have high internal resistance and reduced charge acceptance.

[0008] Therefore, there is a need for further development of enhanced submersible lead-acid batteries, such as enhanced submersible start / stop batteries, that do not undergo stratification during use and / or exhibit a reduced or significant reduction in the level of stratification during use. There is a need for improved enhanced submersible lead-acid batteries that have improved uniformity and performance compared to those used to date, and that have performance comparable to, or even exceeding, that of certain VRLA / AGM batteries. [Overview of the project] [Problems that the invention aims to solve]

[0009] In at least selected embodiments, the present disclosure or invention may address the above-mentioned and other needs. For example, in at least certain embodiments, the present disclosure or invention may cover or provide novel, improved or optimized submersible lead-acid batteries, systems, and enhanced submersible lead-acid battery separators, and methods for manufacturing, testing, and / or using them, and / or vehicles equipped with them. [Means for solving the problem]

[0010] Disclosed herein are novel, improved, or optimized enhanced submersible lead-acid batteries having a specific type of separator. Surprisingly, by appropriately selecting the surface properties of the separator (and optionally together with the orientation of the specific battery plates and separators in the vehicle), stratification can be reduced and / or prevented, correspondingly resulting in increased battery performance, which has been found to be close to, match, or even superior to the performance of a specific VRLA·AGM or VRLA·AGM battery. Furthermore, surprisingly, by using one or more separators described herein together with one or more batteries described herein, and by moving them in use, such movement of the batteries and separators of the invention has been found to promote improved acid mixing or circulation and / or reduction or simultaneous prevention of stratification without requiring any mechanical means or any acid mixing tools (such as an acid mixing pump). Various embodiments are described below in further detail.

[0011] In at least selected embodiments, aspects, or purposes, the Disclosure covers improved lead-acid batteries such as submersible lead-acid batteries, improved systems including lead-acid batteries and battery separators, improved battery separators, improved vehicles including such systems, and / or methods of manufacture and / or use.

[0012] In at least selected embodiments, aspects, or purposes, the Disclosure may provide enhanced submersible lead-acid batteries such as enhanced submersible start / stop batteries that do not undergo stratification during use and / or exhibit reduced or significantly reduced stratification during use, improved uniformity such as acid mixing uniformity compared to those used to date, improved batteries that operate in a partially charged state, and / or improved enhanced submersible lead-acid batteries having performance comparable to or exceeding that of at least certain VRLA·AGM batteries. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 includes a series of photographs comparing cells that have undergone 90 stop / start events or cycles. The top row shows cells with serrated rib separators according to an exemplary embodiment. The bottom row shows cells with conventional solid rib separators extending vertically along the separator. [Figure 2] Figure 2 includes a series of photographs comparing cells that underwent 60 stop / start events or cycles after an overnight period of inactivity. The test cells are equipped with separators similar to those shown in Figure 1, with the top row showing serrated rib separators according to the exemplary embodiment and the bottom row showing cells with conventional solid rib separators. [Figure 3]Figure 3 includes a series of photographs comparing cells that have undergone 90 stop / start events or cycles. The test cells in the top row have separators with serrated ribs that are closer together compared to those shown in Figures 1 and 2. The bottom row has cells with separators that have conventional solid ribs perpendicular to the separator. [Figure 4] Figure 4 includes a series of photographs comparing cells that have undergone 90 stop / start events or cycles. The top row shows cells with dimpled separators according to an exemplary embodiment. The bottom row shows cells with conventional separators that include solid large ribs and solid small ribs extending vertically along the separator. [Figure 5] Figure 5 includes a series of photographs comparing cells that have undergone 90 stop / start events or cycles. The top row shows cells with dimpled separators according to an exemplary embodiment. The bottom row shows cells with separators that include solid ribs extending perpendicularly along the separator coupled with the dimples. [Figure 6] Figure 6 includes a series of photographs comparing cells that have undergone 90 stop / start events or cycles. The top row shows cells with dimpled separators according to an exemplary embodiment, and the bottom row shows cells with separators that include solid ribs extending diagonally along the separator (at a slight angle to the perpendicular direction of the separator). [Figure 7] Figures 7(A) and (B) include comparative photographs of a conventional solid rib separator (A) and no separator at all (B) in a jar filled with a mixed 1.28 specific gravity acid. [Figure 8] Figure 8 includes a photograph of a cell constructed using the serrated rib separator according to this disclosure before inspection for stratification. [Figure 9] Figure 9 includes a photograph of the cells from Figure 8, assembled in a case for stratification testing. Lead straps are placed across groups of electrodes and separators. [Figure 10]Figure 10 includes a photograph of a cross-sectional view of serrations or serrated ribs on a separator used according to various embodiments described herein. [Figure 11] Figure 11 includes two diagrams of the contours of serrated rib separators used according to various embodiments described herein. [Figure 12] Figure 12 shows a graph of the conductivity of a sulfuric acid solution at 25°C (77°F). This graph helps to understand how stratification can lead to non-uniform currents due to differences in conductivity in the high and low acid regions of cells and / or batteries. The graph represents data collected from http: / / myweb.wit.edu / sandinic / Research / conductivity%20v%20concentration.pdf, accessed on July 26, 2016, where conductivity is measured in Siemens / cm and expressed as a function of sulfuric acid solution concentration in weight percent. [Figure 13] Figure 13 includes a photograph of a cell configured similarly to the cell shown in Figure 6. However, for the cell shown in Figure 13, the separator was inserted into a system perpendicular to the direction of vehicle movement. In contrast, for the cell shown in Figure 6, the separator was inserted into a system parallel to the direction of movement. [Figure 14] Figure 14 includes a photograph of a battery separator containing serrated ribs according to various embodiments described herein. This separator was used to enclose electrodes for creating a submersible lead-acid battery for a start / stop vehicle for testing. The results of the testing will be described later. [Figure 15A] Figures 15A(A) and (B) include diagrams of multiple serration contours for separators according to various embodiments herein. Various optimal contours for separators to improve and enhance acid mixing are disclosed herein. The diagrams shown in Figures 15A(A) and (B) are merely examples of such optimal contours, and numerous other optimal contours are described herein and are included within the scope of application of the improved separators, batteries, systems, and methods claimed herein. [Figure 15B] Figures 15B(C) and (D) include diagrams of multiple serration contours for separators according to various embodiments herein. Various optimal contours for separators to improve and enhance acid mixing are disclosed herein. The diagrams shown in Figures 15B(C) and (D) are merely examples of such optimal contours, and numerous other optimal contours are described herein and are included within the scope of application of the improved separators, batteries, systems, and methods claimed herein. [Figure 16] Figure 16 includes a graph showing cycle tests for an example of a reinforced water-immersion battery or a water-immersion battery operating in reinforced mode. [Figure 17A] Figure 17A shows the contour of the horizontal acceleration with lateral or alternating left-right motion, modeled as sinusoidal acceleration experienced by the battery separator for analysis using computational fluid dynamics (CFD). [Figure 17B] Figure 17B shows a visual comparison of a solid rib separator and a serrated rib separator, each subjected to motion defined in Figure 17A for approximately 6 seconds (as shown in the figure), and analyzed using CFD. Both separators analyzed enveloped the positive electrode plate ("positive envelope" or "positive wrapping"). [Figure 18A] Figure 18A shows a solid rib separator subjected to the motion defined in Figure 17A with horizontal acceleration for 60 seconds and analyzed using CFD, illustrating the mixing of the stratified electrolyte in a submersible lead-acid battery. [Figure 18B] Figure 18B shows the volume homogeneity of the acid fraction in the analysis of Figure 18A. [Figure 19A] Figure 19A shows a serrated rib separator subjected to the motion defined in Figure 17A for 60 seconds and analyzed using CFD, illustrating the mixing of the stratified electrolyte in a submersible lead-acid battery. [Figure 19B] Figure 19B shows the volume uniformity of the analysis in Figure 19A. [Figure 20A] Figure 20A shows a comparison of the CFD analyses in Figures 18A and 18B and Figures 19A and 19B. [Figure 20B] Figure 20B shows a comparison of the CFD analyses in Figures 18A and 18B and Figures 19A and 19B. [Figure 21] Figure 21 defines the rocking motion used in CFD analysis of a serrated rib separator. [Figure 22] Figure 22 shows a visual representation of the CFD analysis of a serrated rib separator subjected to the motion described in Figure 21. [Figure 23] Figure 23 is a schematic representation of a separator that encloses ("negative envelope" or "negative wrapping") the negative electrode plate of a water-resistant lead-acid battery, such as an enhanced water-resistant lead-acid battery and / or an ISS water-resistant lead-acid battery. [Figure 24A] Figure 24A is a graph of the CFD analysis of a negatively enveloped serrated rib separator subjected to lateral motion, and is further compared with the graph of the CFD analysis of a positively enveloped serrated rib separator subjected to the same lateral motion. [Figure 24B] Figure 24B is a graphical representation of the volume uniformity of the negative envelope serrated rib separator shown in Figure 24A. [Figure 24C] Figure 24C is a graphical comparison of the volume uniformity of negatively enveloped and positively enveloped serrated rib serrators. [Figure 25A] Figure 25A shows the variables of a segmented rib pattern according to an exemplary embodiment of the present disclosure. [Figure 25B] Figure 25B shows the variables of a segmented rib pattern according to an exemplary embodiment of the present disclosure. [Figure 25C] Figure 25C shows the variables of a segmented rib pattern according to an exemplary embodiment of this disclosure. [Figure 25D] Figure 25D shows the variables of a segmented rib pattern according to an exemplary embodiment of this disclosure. [Figure 25E] Figure 25E shows the variables of a segmented rib pattern according to an exemplary embodiment of this disclosure. [Figure 25F] Figure 25F shows the variables of a segmented rib pattern according to an exemplary embodiment of this disclosure. [Figure 26A]Figures 26A(A) to 26(C) show a battery separator having segmented ribs as defined by the exemplary embodiments of the present disclosure and the patterns shown therein. [Figure 26B] Figure 26B(D) shows a battery separator having segmented ribs as defined by the exemplary embodiment of the present disclosure and the pattern shown therein. [Figure 26C] Figure 26C(E) shows a battery separator having segmented ribs as defined by the exemplary embodiment of the present disclosure and the pattern shown therein. [Figure 26D] Figure 26D(F) shows a battery separator having segmented ribs as defined by the exemplary embodiment of the present disclosure and the pattern shown therein. [Figure 26E] Figure 26E(G) shows a battery separator having segmented ribs as defined by an exemplary embodiment of the present disclosure and the pattern shown therein. [Figure 27A] Figure 27A is a graphical comparison of CFD analyses of a negative-enveloped serrated rib separator and a negative-enveloped divided rib separator subjected to lateral motion. [Figure 27B] Figure 27B shows a comparison of the volume uniformity of multiple CFD analyses of separators subjected to the lateral motion described above. [Figure 28A] Figure 28A is a graphical comparison of CFD analysis results for negative-enveloped solid rib separators and negative-enveloped divided rib separators subjected to lateral motion. [Figure 28B] Figure 28B shows a comparison of the volume uniformity of multiple CFD analyses of solid rib separators, serrated rib separators, and segmented rib separators, all of which are negatively enveloped. [Figure 29A] Figure 29A shows in detail a separator with three divisions of various segmented rib patterns. [Figure 29B] Figure 29B shows the division rib variables for a divided rib separator divided into three sections. [Figure 29C] Figure 29C shows the division rib variables for a single divided division rib separator. [Figure 30A] Figures 30A(A) to (C) show the separator variables for a divided rib pattern divided into multiple sections. [Figure 30B] Figure 30B(D) shows the separator variables for a divided rib pattern divided into multiple sections. [Figure 30C] Figure 30C(E) shows the separator variables for a divided rib pattern divided into multiple sections. [Figure 30D] Figure 30D(F) shows the separator variables for a divided rib pattern divided into multiple sections. [Figure 30E] Figure 30E(G) shows the separator variables for a divided rib pattern divided into multiple sections. [Figure 30F] Figure 30F(H) shows the separator variables for a divided rib pattern divided into multiple sections. [Figure 31] Figure 31 shows a graph of the CFD analysis of negative envelope separators for four different 3-part divided rib patterns. [Figure 32A] Figure 32A is a graphical comparison of CFD analyses of a three-part segmented rib pattern separator subjected to lateral motion and a single-part segmented rib separator subjected to negative envelope (as shown in Figure 26D). [Figure 32B] Figure 32B shows a comparison of the volume uniformity of multiple CFD analyses of separators subjected to the lateral motion described above. [Figure 33A] Figure 33A shows the headspace of a battery having a splash baffle according to an exemplary embodiment of the present disclosure. [Figure 33B] Figure 33B shows the headspace of a battery having a splash baffle according to an exemplary embodiment of the present disclosure. [Figure 33C] Figure 33C shows the headspace of a battery having a splash baffle according to an exemplary embodiment of the present disclosure. [Figure 34A] Figure 34A shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34B]Figure 34B shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34C] Figure 34C shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34D] Figure 34D shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34E] Figure 34E shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34F] Figure 34F shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34G] Figure 34G shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34H] Figure 34H shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 34I] Figure 34I shows an example of a variation from the exemplary embodiment of this disclosure. [Figure 35] Figure 35 shows a separator for a long cell battery having a rib pattern substantially as shown in Figure 26D. [Figure 36] Figure 36 shows the time-varying volume uniformity of the separator shown in Figure 35, compared to the volume uniformity of other separator designs, based on CFD analysis. [Figure 37] Figure 37 shows a comparison of the velocity contour time history of the contour of a tol acid mixture according to Concept 1 of the invention with that of a conventional solid baffled tol contour. [Figure 38] Figure 38 shows an example of a spacer of the invention having, for example, a pattern of segmented ribs installed between a planar separator and an electrode. [Figure 39A] Figure 39A shows an exemplary embodiment illustrating the dimensional values ​​of the power-type separator contour, spacing, and headspace of the invention, for example, within a long battery or battery case. [Figure 39B] Figure 39B shows an exemplary embodiment illustrating the dimensional values ​​of the power-type separator contour, spacing, and headspace of the invention, for example, within a long battery or battery case. [Figure 39C]Figure 39C shows an exemplary embodiment illustrating the dimensional values ​​of the power-type separator contour, spacing, and headspace of the invention, for example, within a long battery or battery case. [Figure 40] Figure 40 shows a contour prototype of the acid mixture contour of the illustrative invention. [Figure 41] Figure 41 shows a contour prototype of the acid mixture contour of the illustrative invention. [Figure 42] Figure 42 includes an image demonstrating the mixed advantage of the invention's contour compared to the contour of conventional solid ribs. [Modes for carrying out the invention]

[0014] In various embodiments described herein, separators are used to enhance electrolyte mixing and / or circulation in submersible lead-acid batteries. In certain embodiments, separators are used to reduce stratification. In various embodiments, lead-acid batteries are disclosed in which stratification is significantly reduced compared to known batteries, due to improved or enhanced separators or separator systems for acid mixing and to prevent or at least reduce stratification and the adverse effects of stratification. Such batteries may be used, for example, in a moving vehicle having a battery. Also in various embodiments, the movement of a vehicle (e.g., an electric vehicle or partially electric vehicle including a start / stop lead-acid battery) for actually mixing the acid or electrolyte, in combination with the enhanced battery separators described herein, unexpectedly results in a significant reduction in stratification as shown herein, as well as a significant improvement in acid mixing as shown herein, in start / stop submersible lead-acid batteries and / or enhanced submersible lead-acid batteries or batteries operating in enhanced mode. For example, the stopping and starting of a start / stop electric vehicle is powered by various embodiments herein, which involves mixing the acid / electrolyte in a reinforced submersible lead-acid battery, improving the acid mixture, and reducing or completely preventing stratification.

[0015] The exemplary embodiments of separators described herein (preferably reinforced acid-mixed separators, leaves, sleeves, wraps, pockets, or envelopes) are preferably porous membranes made of suitable natural or synthetic materials such as polyolefins, polyethylene, polypropylene, phenolic resins, polyvinyl chloride (PVC), rubber, synthetic pulp (SWP), glass fibers, cellulosic fibers, or combinations thereof (such as microporous membranes, mesoporous membranes, or macroporous membranes, porous polymer membranes, or porous-filled polymer membranes with pores smaller than about 1 μm), and more preferably microporous membranes made of thermoplastic polymers. Suitable microporous membranes may have a pore diameter of about 0.1 μm (100 nm) and a porosity of about 60%. The thermoplastic polymers may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. Suitable thermoplastic polymers include polyvinyl and polyolefin. Polyvinyl includes, for example, PVC. Polyolefins include, for example, polyethylene, ultra-high molecular weight polyethylene (UHMWPE), and polypropylene. A preferred embodiment may include a mixture of a filler (e.g., silica) and UHMWPE. Generally, a preferred separator may be made by mixing about 30% by weight of silica with about 10% by weight of UHMWPE and about 60% of process oil in an extruder. The mixture may also contain small amounts of other additives or agents common in separator technology (such as wetting agents, colorants, antistatic agents, similar materials, or combinations thereof) that are extruded in the form of a flat sheet. A preferred polyolefin separator may be a silica-filled microporous sheet of polyolefin (with or without residual oil and one or more additives or surfactants) having one or more serrated ribs, protrusions, embroidery, dimples, embossing, and combinations thereof on its surface (preferably which may result in an acid mixing effect due to electrolyte oscillation caused by vehicle movement).

[0016] The separator is preferably made of polyolefin, such as polypropylene, ethylene-butene copolymer, preferably polyethylene, more preferably high molecular weight polyethylene, for example polyethylene having a molecular weight of at least 600,000, or high-density polyethylene, for example polyethylene having a molecular weight of at least 500,000. Depending on the embodiment, one or more ultra-high molecular weight polyethylenes may be used. For example, polyethylene having a molecular weight of at least 1,000,000, particularly more than 4,000,000, and possibly 5,000,000 to 8,000,000 (measured by viscosity measurement and calculated by Margolies' equation), a standard load melt index of virtually 0 (as specified and measured in ASTM D1238 (condition E) using a standard load of 2,160 g), and a viscosity number of 600 ml / g or higher, preferably 1,000 ml / g or higher, more preferably 2,000 ml / g or higher, and most preferably 3,000 ml / g or higher (determined by a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C).

[0017] According to at least one embodiment, the separator comprises ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil and silica, for example, precipitated silica and / or fumed silica. According to at least one other embodiment, the separator comprises ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil, additives and silica, for example, precipitated silica. The separator preferably comprises a homogeneous mixture of 8 to 100 volume% polyolefin, 0 to 40 volume% plasticizer, and 0 to 92 volume% inert filler. In some cases, a suitable filler is dry, finely fragmented silica. However, the fillers may be selected from the following group: silica, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, clay, aluminum silicate, sodium aluminum silicate, aluminum polysilicate, alumina silica gel, glass particles, carbon black, activated carbon, carbon fiber, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, lead oxide, tungsten, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate, magnesium carbonate, etc., and various combinations thereof.

[0018] Suitable plasticizers are petroleum, wax, or a combination thereof. Since plasticizers are the easiest components to remove from polymer-filler-plasticizer mixtures, they are useful in imparting porosity to the battery separator. Pores may also be formed by other processes or materials, such as by removing particles.

[0019] The separator has an average pore size of less than 5 μm in diameter, preferably less than 1 μm. Preferably, more than 50% of the pores have a diameter of 0.5 μm or less. Preferably, at least 90% of the pores have a diameter of less than 0.9 μm. The microporous separator preferably has an average pore size in the range of 0.05 to 0.9 μm, and in some cases, 0.1 to 0.3 μm.

[0020] Pore ​​size may, in some cases, be measured using the mercury intrusion method described in Ritter, HL, and Drake, LC, Industrial and Technical Chemistry Analysis, 17th edition, 787 (1945). According to this method, mercury is introduced into pores of different sizes by varying the pressure applied to the mercury using a porosimeter (Porosimeter Model 2000, Carlo Erba). The pore distribution may be determined by evaluating unanalyzed data using MILESTONE200 software.

[0021] The thickness of the separator is preferably greater than 0.1 mm and 5.0 mm or less. The thickness of the separator can be in the range of 0.15 to 2.5 mm, 0.25 to 2.25 mm, 0.5 to 2.0 mm, 0.5 to 1.5 mm, or 0.75 to 1.5 mm (such thicknesses take into account the overall thickness of the separator, including any ribs, protrusions, dimples, etc.). In some cases, the separator may be about 0.8 mm or 1.1 mm thick. The separator may or may not have one or more thin plates or any other layers (e.g., a nonwoven fabric layer and / or an AGM layer) attached to its surface. Also, one or both electrodes may be wrapped in one or more layers of glass mat or glass fiber and / or a perforated plate wrap.

[0022] In various preferred embodiments, the microporous polyolefin separator layer includes ribs such as serrations, embrasures, angular ribs, or segmented ribs, or a combination thereof. Preferred ribs may be 8 μm to 1 mm high and spaced 1 μm to 20 mm apart. On the other hand, the preferred backweb thickness of the microporous polyolefin separator layer (without ribs or embossing) may be about 0.05 mm to about 0.50 mm (for example, about 0.25 mm in certain embodiments). For example, the ribs may be spaced 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, 2.0 mm, 2.25 mm, 2.5 mm, 2.75 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, or 10 mm apart. Depending on the embodiment, the ribs may be arranged in a pattern such that they are at an angle of 0° to 90° to each other and are located on one side of the separator layer or on both sides of the polyolefin separator. Depending on the embodiment, the acid-mixed ribs may be front, positive, or positive electrode side ribs. Various patterns including ribs on both sides of the separator or separator layer may include positive ribs and negative longitudinal or transverse ribs on the second or back surface of the separator, such as smaller, more closely spaced negative longitudinal or transverse ribs or mini-ribs. Such negative longitudinal or transverse ribs may, in some cases, have a height of about 0.025 mm to about 0.1 mm, preferably about 0.075 mm, but may also be as small as 0.25 mm. Other patterns may include ribs on both sides of the separator layer, with negative mini-ribs (mini-ribs extending in the same direction as the lateral direction compared to the main ribs on the other surface of the separator) on the second or back surface of the separator. Such negative mini-ribs may, in some cases, have a height of about 0.025 mm to about 0.25 mm, preferably about 0.050 mm to about 0.125 mm.

[0023] The ribs may have serrations in certain preferred embodiments. The serrations may have an average tip length of about 0.05 mm to about 1 mm. For example, the average tip length may be 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0024] The serrations may have an average baseline length of approximately 0.05 mm to approximately 1 mm. For example, the average baseline length may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0025] If serrations are present, they may have an average height of approximately 0.05 mm to approximately 4 mm. For example, the average height may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less. In embodiments where the height of the serrations is the same as the height of the ribs, the serrated ribs may be called projections. Such a range may also apply to separators for industrial start / stop main batteries, the overall thickness of which the separator may typically be approximately 1 mm to approximately 4 mm. Similarly, automotive start / stop batteries may have a slightly thinner overall thickness (e.g., typically approximately 0.3 mm to approximately 1 mm).

[0026] The serrations may have an average center-to-center pitch of approximately 0.1 mm to approximately 50 mm. For example, the average center-to-center pitch may be approximately 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm or more, and / or approximately 1.5 mm, 1.25 mm, 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm or less.

[0027] The serrations may have an average height-to-base-to-base ratio of approximately 0.1:1 to approximately 500:1. For example, the average height-to-base-to-base ratio may be approximately 0.1:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, or 450:1 or higher, and / or approximately 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, or 25:1 or lower.

[0028] Serrations can have an average sole-to-tip width ratio of approximately 1000:1 to approximately 0.1:1. For example, the average sole-to-tip width ratio can be approximately 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 or higher. The ratios may be approximately 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or less than or equal to 1:1.

[0029] Depending on the embodiment, the separator may have dimples. Dimples are typically protruding features or lumps on one or more surfaces of the separator. The thickness of the dimples can be 1 to 99% of the thickness of the separator. For example, the average thickness of the dimples may be about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or less than 5% of the average thickness of the separator. The dimples may be arranged in rows along the separator. The rows or lines may be spaced about 1 μm to about 10 mm apart. For example, the rows may be spaced approximately 0.05mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2.0mm, 2.25mm, 2.5mm, 2.75mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, or 10mm apart. The dimples, on the other hand, may be arranged randomly or randomly placed.

[0030] The dimples may have an average dimple length of approximately 0.05 mm to approximately 1 mm. For example, the average dimple length may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0031] The dimples may have an average dimple width of approximately 0.01 mm to approximately 1.0 mm. For example, the average dimple width may be approximately 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or approximately 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0032] The dimples may have an average center-to-center pitch of approximately 0.10 mm to approximately 50 mm. For example, the average center-to-center pitch may be approximately 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, or 1.5 mm or more, and / or approximately 1.5 mm, 1.25 mm, 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, or 0.2 mm or less.

[0033] The dimples can be, for example, squares and rectangles. The dimples can have an average dimple length-to-dimple width ratio of approximately 0.1:1 to approximately 100:1. For example, the average length-to-width ratio can be approximately 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 450:1, 500:1, 550:1, 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 and above, and / Alternatively, the ratios may be approximately 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 50:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or less than 1:1.

[0034] Depending on the embodiment, the dimples may be substantially circular. Circular dimples may have a diameter of about 0.05 to about 1.0 mm. For example, the average dimple diameter may be about 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, or 0.9 mm or more, and / or about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less.

[0035] Other shapes of dimples may also be included. Just as an example, such dimples may be triangular, pentagonal, hexagonal, heptagonal, octagonal, oval, elliptical, and combinations thereof.

[0036] In some embodiments, the separator may feature a combination of ribs, serrations, dimples, or a combination thereof. For example, the separator may have a series of serrated ribs extending from top to bottom along the separator, and a second series of serrated ribs extending horizontally along the separator. In other embodiments, the separator may have an alternating sequence of serrated ribs, dimples, continuous, intermittent, or segmented solid ribs, or a combination thereof.

[0037] Table 1 includes, but is not intended to limit, several specific embodiments of serrations and / or dimples and separators having various parameters used in forming separators to prevent stratification and enhance acid mixing in submersible lead-acid batteries (sometimes called reinforced submersible batteries).

[0038] [Table 1]

[0039] The separators disclosed herein preferably provide enhanced electrolyte mixing and / or acid circulation compared to conventional separators. In certain embodiments, the separator provides less stratification, such as measured by electrolyte concentrations at the top and bottom of the cell. The concentration difference may be less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, or 1% after the cell has undergone 30, 60, 90 or more start / stop events or cycles. In certain selected embodiments, the concentration difference may be less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 2.5%, or 1% after the cell has remained stationary for 24, 48, 72 or more times.

[0040] In some embodiments, the improved separator may include a coating on one or both sides. Such a coating may include a surfactant or other material. In some embodiments, the coating may include one or more materials, for example, as described in U.S. Patent Publication No. 2012 / 0094183, which is incorporated by reference herein. Such a coating may, for example, reduce the overcharge voltage of the battery system, thereby reducing grid corrosion, extending battery life, and preventing drying and / or moisture loss.

[0041] The separators used in the various embodiments described herein may comprise one or more additives, for the additives may enhance the separator for a particular stop / start submersible lead-acid battery for a particular vehicle. One such additive present in polyolefins is a surfactant. Other such additives may comprise one or more latex additives. Suitable surfactants include alkyl sulfates, alkylaryl sulfonates, alkylphenol-alkylene oxide addition products, etc. The surfactants include soap, alkylnaphthalene sulfonates, dialkyl esters of sulfosuccinates, quaternary amines, block copolymers of ethylene oxide and propylene oxide, and salts of mono and dialkyl phosphate esters. Additives may include alkyl polysaccharides such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated fatty alcohols, alkyl polyglycosides and their blends, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters, and sucrose fatty acid esters.

[0042] In certain embodiments, the additive can be represented by the following compounds: Equation (I) = R(OR) 1 ) n (COOM x+ 1 / x ) m (I) Here, R is a non-aromatic hydrocarbon group having 10 to 4200 carbon atoms, preferably 13 to 4200 carbon atoms, which can be blocked by an oxygen atom. R1 is H, -(CH2)kCOOMx+1 / x or -(CH2)k-SO3MX+1 / X, preferably H, where k=1 or 2. M is an alkali metal or alkaline earth metal ion, H+ or NH4+, where not all variables M simultaneously represent H+. n = 0 or 1. m = 0 or an integer between 10 and 1400. x = 1 or 2. Here, the oxygen-to-carbon atom ratio in the compound according to equation (I) is in the range of 1:1.5 to 1:30, and m and n cannot be 0 at the same time. However, preferably, only one of the variables n and m is not 0.

[0043] A non-aromatic hydrocarbon group is intended, which does not contain an aromatic group or represents itself. The hydrocarbon group can be interrupted by an oxygen atom, i.e., contains one or more ether groups.

[0044] R is preferably a linear or branched aliphatic hydrocarbon group that can be interrupted by an oxygen atom. A saturated, unbridged hydrocarbon group is highly preferred.

[0045] By using the compound of formula (I) in the production of various additives for battery separators described herein, effective protection against oxidative destruction may be provided to such separators. In some embodiments, a battery separator comprising an additive containing a compound according to formula (I) is preferred. Here, R is a hydrocarbon group having 10 to 180, preferably 12 to 75, and very preferably 14 to 40 carbon atoms that can be interrupted by 1 to 60, preferably 1 to 20, and very preferably 1 to 8 oxygen atoms, particularly preferably of the formula R 2 -[(OC2H4) p (OC3H6) q - hydrocarbon group. Here, R is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 2 carbon atoms. P is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4. q is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4. The compound is particularly preferred when the sum of p and q = 0 to 10, especially 0 to 4. n = 1. m = 0.

[0046] For the formula R 2 -[(OC2H4) p (OC3H6) q - although these are compounds, the square brackets It is understood that this includes compounds in which the sequence of groups in parentheses differs from that shown. For example, according to this disclosure, compounds in which the groups in parentheses are substituted with (OC2H4) and (OC3H6) groups are also appropriate.

[0047] R 2 A linear or branched alkyl group having 10 to 20, preferably 14 to 18, carbon atoms. The additives described above have proven to be particularly advantageous. OC2H4 preferably represents OCH2CH2, and OC3H6 represents OCH(CH3)CH2 and / or OCH2CH(CH3).

[0048] As suitable additives, alcohols (p=q=0, m=0) may be mentioned in particular. Primary alcohols are particularly preferred, and fatty alcohol ethoxylates (p=1-4, q=0), fatty alcohol propoxylates (p=0, q=1-4), and aliphatic alcohol alkoxylates (p=1-2, q=1-4) of primary alcohols are preferred. Aliphatic alcohol alkoxylates can be obtained, for example, through the reaction of the corresponding alcohol with ethylene oxide or propylene oxide.

[0049] Additives of type m=0 that are insoluble or partially soluble in water and sulfuric acid have proven to be particularly advantageous.

[0050] Additives containing compounds according to formula (I) are also preferred. Here, R is an alkane group having 20 to 4200 carbon atoms, preferably 50 to 750 and very preferably 80 to 225 carbon atoms. M is an alkali metal or alkaline earth metal ion, H + or NH4 + In particular, Li + na + and K + or H + These are alkali metal ions, and all variables M are simultaneously H + It has the meaning of That's not the case. N=0. m is an integer between 10 and 1400. x = 1 or 2.

[0051] Suitable additives may include polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers, in particular, where at least some of the acid groups are neutralized, for example, preferably 40%, and especially preferably 80%. The percentage refers to the number of acid groups. Polyacrylic acid (polymethacrylic acid) present as a whole in salt form is very preferred. Polyacrylic acid (polymethacrylic acid) is intended to be polyacrylic acid, polymethacrylic acid, and acrylic acid-methacrylic acid copolymers. The average molar mass M of polyacrylic acid (polymethacrylic acid) is particularly 1,000 to 100,000 g / mol, especially preferably 1,000 to 15,000 g / mol, and very preferably 1,000 to 4,000 g / mol. w Polyacrylic acid having the following properties is preferred. The molecular weight of polyacrylic acid (polymethacrylic acid) polymers and copolymers can be determined by measuring the viscosity of a 1% aqueous solution neutralized with a sodium hydroxide solution of the polymer (Fikencher's constant).

[0052] Copolymers of acrylic acid (methacrylic acid), particularly copolymers containing ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate as comonomers in addition to acrylic acid (methacrylic acid), are also suitable. Copolymers containing at least 40% by weight, preferably at least 80% by weight, of acrylic acid (methacrylic acid) monomers are preferred, with the proportion based on the acidic form of the monomer or polymer.

[0053] To neutralize polyacrylic acid polymers and copolymers, alkali metals and alkaline earth metal hydroxides such as potassium hydroxide and especially sodium hydroxide are particularly suitable.

[0054] Microporous polyolefins may contain additives or a combination of additives in various ways. Additives can be applied to the polyolefin, for example, at the time of completion (e.g., after extraction) or when added to a mixture used to produce the polyolefin. According to a preferred embodiment, The additive or a solution of the additive is applied to the surface of the polyolefin. This variant is particularly suitable for applying non-thermally stable additives and additives that are easily soluble in solvents used for subsequent extraction. Particularly suitable solvents for the additives according to this disclosure are low molecular weight alcohols such as methanol and ethanol, as well as mixtures of these alcohols with water. The application may be applied to the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides.

[0055] The additive should be at least 0.5 g / m 2 1.0 g / m 2 1.5g / m 2 2.0g / m 2 2.5g / m 2 3.0g / m 2 3.5g / m 2 4.0g / m 2 4.5g / m 2 , 5 0.0g / m 2 5.5g / m 2 6.0g / m 2 6.5g / m 2 7.0g / m 2 , 7.5 g / m 2 8.0g / m 2 8.5g / m 2 9.0g / m 2 9.5g / m 2 or 10.0 g / m 2 It can be present at concentrations of 0.5-10 g / m³. The additive is present in concentrations of 0.5-10 g / m³. 2 , 1.0~10.0g / m 2 1.5~10.0g / m 2 , 2.0~10.0g / m 2 2.5~10.0g / m 2 3.0~10.0g / m 2 3.5~10.0g / m2 4.0~10.0g / m 2 4.5~10.0g / m 2 5.0~10.0g / m 2 5.5~10.0g / m 2 6.0~10.0g / m 2 6.5~10.0g / m 2 7.0~10.0g / m 2 7.5~10.0g / m 2 5.0~10.5g / m 2 5.0~11.0g / m 2 5.0~12.0g / m 2 , or 5.0~15.0 g / m 2 It can be present in the separator at intermediate concentrations.

[0056] The coating may be applied by roller-applying the additive or a solution of the additive to the polyolefin, or by immersing the polyolefin in the additive or a solution of the additive and then optionally removing the solvent (e.g., by drying). The coating may also be applied by any other known method. In this way, the coating of the additive can be combined with extraction, for example, which is often performed during the production of polyolefins.

[0057] The following photographic examples in Figures 1-7B visually represent acid-base electrolytes containing a red dye within the acid, and distinguish them from those with high acid concentration and high pH levels.

[0058] Referring to Figure 1, a series of photographs are shown comparing a cell having a serrated or engagement rib separator according to an exemplary embodiment (top row) with a cell having a conventional solid rib separator extending perpendicularly along the separator (bottom row). The spacing of the engagement ribs (rib tip to rib tip) relative to the separator shown in the top row was approximately 11 mm. Figure 1 shows the surface of the battery separator facing the positive electrode of a submersible lead-acid battery, such as a partially charged submersible lead-acid battery. However, such ribs may instead face the negative electrode, or may be included on both sides of the separator (for example, on the surface of a separator designed to face the negative electrode of a submersible lead-acid battery). The cell shown in Figure 1, with a separator and enveloped electrodes parallel to the direction of motion, underwent 90 start / stop events or cycles. As shown in Figure 1, after 30, 60, and 90 start / stop events or cycles, the stratification exhibited by cells with serrated rib separators is significantly less than that of cells with conventional separators.

[0059] Referring to Figure 2, a series of photographs are shown comparing cells of the same type as those shown in Figure 1. The cells underwent 60 start / stop events or cycles in a vehicle traveling at 25 mph after being stationary overnight. The top row shows cells with serrated-rib separators according to an exemplary embodiment. The bottom row, on the other hand, shows cells with conventional separators with solid ribs. As shown in Figure 2, the stratification exhibited by the cells with serrated-rib separators is significantly less than that of the cells with conventional separators. Such testing validated the experimental results shown in the photographs of Figure 1.

[0060] Moving to Figure 3, cells with closerly spaced serrated rib separators according to the exemplary embodiment (top row) were compared to cells with conventional solid rib separators perpendicular to the separators (bottom row). The spacing of the engagement ribs relative to the separators shown in the top row was approximately 7 mm. The cells underwent 90 start / stop events or cycles. As shown in Figure 3, after 30, 60, and 90 start / stop events or cycles, the stratification exhibited by the cells with serrated rib separators was significantly less than that of the cells with conventional separators.

[0061] Referring to Figure 4, a series of photographs show a comparison between a cell with a dimpled separator according to an exemplary embodiment (top row) and a cell with a conventional separator that includes large and small solid ribs extending vertically along the separator (bottom row). The cells underwent 90 start / stop events or cycles. As shown in Figure 4, after 30, 60, and 90 start / stop events or cycles, the stratification exhibited by the cell with the dimpled separator is significantly less than that of the cell with the conventional separator. Thus, solid ribs, such as those shown in the photographs in the bottom row of Figure 4, effectively inhibit acid mixing to the separator in an idle start / stop lead-acid battery.

[0062] Referring to Figure 5, a series of photographs shows a comparison between a cell having a dimpled separator according to an exemplary embodiment (top row) and a cell having a separator containing solid ribs extending perpendicularly along the dimpled and coupled separator (bottom row). The cells underwent 90 start / stop events or cycles. As shown in Figure 5, the stratification shown in the cell with the dimpled separator (top row) is less than that of the start / stop lead-acid battery cell in the bottom row having a separator containing a combination of dimples and solid ribs. However, compared to the bottom row in the photographs of Figures 1-4, for example, some acid mixing is shown in the bottom row. For example, in some of the photographs in the bottom row, distinct areas or pockets of low acid concentration are visible, but acid mixing is also seen. The photographs in the bottom row suggest that combinations of serrations and solid ribs or dimples and solid ribs may prove useful in the various batteries, systems, and methods relating to this disclosure.

[0063] Referring to Figure 6, there is a series of photographs comparing a cell with a dimpled separator according to an exemplary embodiment (top row) with a cell having a separator that includes solid ribs extending diagonally along the separator at a slight angle to the perpendicular direction of the separator. The cell underwent 90 start / stop events or cycles. As shown in Figure 6, the stratification shown in the cell with the dimpled separator (top row) is less than that of the start / stop lead-acid battery cell in the photographs, such as those shown in the bottom row of Figures 1-4. Regarding the bottom row of photographs in Figure 6, some stratification can still be seen after 60 cycles or 60 start / stop events, but the stratification improves after 90 cycles.

[0064] Figures 7A and 7B include comparative photographs of a conventional solid-rib separator (Figure 7A) and no separator at all (Figure 7B) in a jar filled with an acid having a specific gravity of 1.28. Figure 7A shows a photograph of the conventional ribbed separator, with stratification indicated by the concentration of red acid at the bottom of the jar and the clear liquid towards the top of the jar. Figure 7B shows a photograph of only the lead grid electrodes without a separator, with much less stratification occurring, as indicated by the red color across the jar. Figures 7A and 7B help illustrate that conventional separators with solid ribs may hinder acid mixing and promote stratification inside start / stop submersible lead-acid batteries. Similarly, Figure 7B provides a form of benchmark without a separator, against which various separators can be compared and contrasted.

[0065] Figure 8 includes a photograph of a cell constructed using the serrated rib separator according to this disclosure before inspection for stratification.

[0066] Figure 9 includes a photograph of the cell from Figure 8 assembled in a case for stratification testing. Lead straps are placed across the group of electrodes and separators. Once the acid is added to the case, the acid level may be several millimeters above these lead straps (in one example, possibly about 3 mm above the lead straps). When this case, including the electrodes and separators, is tested for stratification within the cell, in certain embodiments, the direction of the test movement is preferably to mimic the movement of a start / stop electric vehicle. The movement is therefore substantially parallel to the plate and separators in the photograph, so that the acid is moved across the surface of the electrodes as the vehicle is moved, accelerated, decelerated, and / or stopped. Figure 9 may appear as if the top of the photograph extends toward the front bumper of an electric vehicle with start / stop capabilities, while the bottom of the photograph in Figure 9 extends toward the rear bumper of the same electric vehicle, overlooking the group of electrodes, separators, and lead straps that will soon be filled with acid for stratification testing. In other words, the electrodes and separators are parallel to the movement created in the test.

[0067] Figure 10 includes a photograph of a cross-sectional view of serrations or serrated ribs on a separator used according to various embodiments described herein.

[0068] Figure 11 includes two diagrams of the contours of serrated separators used according to various embodiments described herein.

[0069] Figure 12 shows a graph of the conductivity of a sulfuric acid solution at 25°C. This graph helps to understand how stratification can lead to non-uniform currents due to differences in conductivity in the high and low acid regions of cells and / or batteries.

[0070] Figure 13 includes a photograph of a cell configured similarly to the cell shown in Figure 6. However, with respect to the cell shown in Figure 13, the separator was inserted into a system perpendicular to the direction of vehicle movement. On the other hand, with respect to the cell shown in Figure 6, the separator was inserted into a system parallel to the direction of movement, as described in the direction in Figure 9 above. In various embodiments, it is preferable that the separator be positioned parallel to the direction of movement relative to the vehicle and battery system. This is because the photograph shown in Figure 13 clearly shows that stratification is still occurring after 60 start / stop events or cycles without good acid mixing. Using the top row of Figure 13 as an example, there, a dimpled separator is used according to various embodiments of this disclosure, but stratification is still occurring and acid mixing is not optimal.

[0071] Figure 14 includes a photograph of a battery separator containing serrated ribs according to various embodiments described herein. This separator was used to enclose electrodes for creating a submersible lead-acid battery for a start / stop vehicle for testing. The results of the testing will be described later.

[0072] Figures 15A–15D include diagrams of multiple serration contours for separators according to various embodiments herein. Various optimal contours for separators to improve and enhance acid mixing are disclosed herein. The diagrams shown in Figures 15A–15D are merely examples of such optimal contours. Numerous other optimal contours are included within the scope of application of the improved separators, batteries, systems, and methods described herein.

[0073] Figure 16 shows an example of a reinforced water-resistant battery or a water-resistant battery operating in reinforced mode. The graph includes a graph showing cycle testing. In today's newer battery applications, enhanced water-immersion batteries operate at lower charge levels than previously known water-immersion lead-acid batteries, which are often operated at overcharged or more than 100% charge levels. Thus, such enhanced water-immersion batteries may operate at charge levels (SoC) of less than 95%, possibly less than 90%, possibly less than 85%, possibly less than 80%, and even less than 70%, possibly less than 60%, possibly less than 50%, possibly less than 25%, and possibly less than 10%. In this particular graph, cycle testing was performed on a battery with a depth of discharge (DoD) of 17.5%, and the separator used was a conventional ribbed separator, as shown in the bottom row of the photograph in Figure 1. This particular battery demonstrated the ability to deliver energy and perform well in a lead sulfate-rich environment under high cycle conditions at a partially discharged charge level. As shown in Figure 16, batteries such as those used in start / stop applications dramatically increased energy throughput compared to standard SLI batteries (such as those specified in standards like EN50342). Since such enhanced submersible and / or submersible batteries for start / stop applications operate in a partially charged state, they need to have higher charging efficiency and / or charge more quickly. In some cases, enhanced submersible batteries are created using various additives along with one or more electrodes to increase charging efficiency and / or charge more quickly. However, the enhanced separators described herein can achieve the same goal.

[0074] The separators, methods, batteries, and battery systems described herein may reduce stratification and improve electrolyte circulation and mixing over long periods of time. This is particularly important for deep-circulating and / or enhanced submersible lead-acid batteries, where stratification can significantly reduce battery performance. Various submersible lead-acid batteries, enhanced submersible lead-acid batteries, and their applications may benefit from the improved separators, methods, batteries, and systems described herein. Various start / stop vehicles, including but not limited to various electric vehicles, automobiles, hybrid vehicles, fork trucks, golf carts, neighborhood electric vehicles, etc., in particular vehicles and / or batteries that are not fully charged and are in a partially charged state may benefit from the improved separators, batteries, battery systems, and methods described herein.

[0075] Exemplary embodiments of the enhanced immersion separators described herein, known as acid-mixed separators, may be used in enhanced immersion batteries, particularly mobile batteries, and surprisingly and unexpectedly, bring about a significant improvement in acid mixing and / or acid circulation in such enhanced immersion batteries, resulting in a significant reduction or complete prevention of stratification within the enhanced immersion battery. This may be critical because the flow and circulation of acid along the entire separator means that the entire battery is utilized for several smaller parts of the battery in use. That is, with the enhanced separators, batteries, systems, and methods of the present disclosure, the electrolyte (e.g., sulfuric acid) flows freely to and along all or almost all parts of the separator, and therefore freely to and along all or almost all parts of the positive and negative electrode active materials of the electrodes. On the other hand, stratification (see stratification in the lower row of the photographs in Figures 1-4 as just one example, where red indicators are added to the acid; the clear liquid, i.e., water, is clearly visible and present in the upper half of the test cell, while the acid is clearly visible and present in the lower half of the test cell) causes the entire separator, and therefore the entire positive and negative electrode active material on either side of such a separator, to be completely lacking in acid, and thus unable to power the underlying device / vehicle using the battery to its maximum potential. Therefore, the improved separators, batteries, systems, and methods described herein greatly reduce stratification in submersible lead-acid batteries, such as enhanced submersible batteries.

[0076] The reason for concern regarding stratification is that it results in non-uniform current density across the surfaces of the positive and negative plates or electrodes. The graph shown in Figure 12 shows the conductivity of H2SO4 as a function of sulfuric acid concentration by weight percentage.

[0077] In some preferred embodiments of this disclosure, the serrations, dimples, and / or segmented ribs present on one or more surfaces of the separator are unevenly distributed. Furthermore, in some preferred embodiments, the serrations, dimples, and / or segmented ribs present on one or more surfaces of the separator differ in specific sections or regions on at least one surface of the separator. For example, the serrations and dimples themselves may be uneven in size (e.g., randomly formed), and the spacing between the serrations and / or dimples may be random and / or uneven. For example, the various serrations and / or dimples used herein may be present on one or both surfaces of the separator in regular or irregular arrangements. Furthermore, the various ribs used herein, such as serrated ribs, may be nonlinear. For example, some serrated ribs may have a wavy pattern or a nonlinear pattern.

[0078] In various embodiments, the effectiveness of the reinforced immersion separator for reinforced immersion batteries described herein is particularly pronounced when the separator is positioned within the reinforced immersion battery such that the reinforcement of the separator extends parallel to the direction of motion of the moving battery. Such an effect can be understood by comparing the desirable result in Figure 6 with the less desirable result in Figure 13. In the photograph of Figure 13, stratification is still observed despite the use of a separator with a reinforced contour for acid mixing. This is because the cell in Figure 13 is positioned such that the reinforcement in the separator and electrodes is perpendicular to the direction of motion of the battery in the vehicle. In some cases, the arrangement of the battery in the vehicle with electrodes and separators parallel to the start and stop inertia may allow for better acid mixing than perpendicular positioning.

[0079] The various reinforced separators described herein, such as reinforced separators having serrations to improve acid mixing and acid circulation, may have varying spacing and / or patterns. As just one example, Figures 15A–15D show examples of serrated ribs that may be effective in exemplary embodiments. Such patterns, and other patterns (both uniform and non-uniform, and both regular and irregular), may also enable improvements in cold cranking amperage (CCA) in submersible lead-acid batteries, as well as other major improvements in the electrical properties of the battery. As just one example, a serrated pattern like that in Figures 15A–15D reduces the surface area by about 53% compared to a separator with solid ribs (controlling means) that allows for a reduction in the ribs in contact with the positive electrode active material (PAM), resulting in improved CCA performance. In such patterns, as shown in Figures 15A–15D, the mass of the ribs may be reduced by 33% compared to a solid rib contour (controlling means) that can increase acid utilization and improve performance. Furthermore, it may be important to maintain the compression of the positive electrode active material (PAM) by balancing the mass and opening of the ribs for acid mixing and acid utilization.

[0080] Furthermore, the arrangement and design of protrusions (such as dimples and serrations) must be optimized for compression so as not to promote PAM discharge, and preferably they should be supported across the grid frame so as not to push the pellets out of close proximity to the grid frame or current collector.

[0081] The batteries of this disclosure may be provided to reduce costs by reducing the amount of lead required for superior performance resulting from the increased use of PAM. In addition, in this way, automotive manufacturers This could potentially lead to cost reductions for batteries, which is a demand from the automotive industry, as well as weight reductions for batteries, which is also a demand from automakers.

[0082] In some cases, the reinforced separators used in this disclosure may have an optimized rib profile having a rib surface area compared to the rib surface area of ​​a conventional rib profile, such as a solid vertical rib profile having a rib surface area of ​​10-90%, preferably 30-70%, and more preferably, optionally 40-60% of the surface area of ​​a conventional rib profile. All of this is determined by the rib shape, rib spacing, and the ultimate goal of improving acid mixing and preventing stratification, and all of these are optimized.

[0083] (example) Figures 8 and 9 show battery experiments conducted in cell containers. The battery test cells shown in these photographs, along with the white cases and lead electrode groups, had the following general characteristics.

[0084] [Table 2]

[0085] In the additional examples shown below, commercial group 31 19 plate / group Ca / Ca shows extended battery test data. In this table, separators labeled "novel" have the serration contour shown in the envelope in Figure 14. On the other hand, results labeled "controlled" have solid ribs perpendicular to the separator. These results reveal unexpected and / or surprising results regarding the improvement in battery performance for start / stop reinforced submersible lead-acid batteries using the reinforced separators of this disclosure. The results in the table below showed significant improvement even when the batteries were not installed with significant movement inside a vehicle, but rather with general movement while moving around in a test facility. Thus, combined with the energy from movement from the vehicle and / or various start / stop events, the battery performance results may improve even more significantly.

[0086] [Table 3]

[0087] The CFD examples described in Figures 18A-32B show cells in short batteries, such as those used in ISS, SLI, or golf car batteries. The CFD examples described in Figures 35-37 and 39 show cells in long batteries, such as those used in the power vehicle industry, for example, in forklift batteries.

[0088] An example of a short cell shows a separator with a width of approximately 142 mm, a height of approximately 129 mm, a back web thickness of approximately 250 μm, and a rib height of approximately 600 μm. The example of a short cell also shows that there is approximately 3 mm between either side of the separator and the side wall boundary of the battery case, and the headspace on the separator is approximately 44 mm.

[0089] An example of a long cell shows a separator with a width of approximately 158 mm, a height of approximately 406 mm, a back web thickness of approximately 500 μm, and a rib height of approximately 1.8 mm. The example of a long cell also shows a distance of approximately 3 mm between either side of the separator and the side wall boundary of the battery case, with the head space on the separator. This indicates that the length is approximately 51mm.

[0090] The significance of this Midtronics CCA test lies in the fact that, although it is not a global standard test, it is a handheld device that uses an algorithm to quickly and easily calculate battery performance. By increasing the surface area of ​​the positive lattice exposed to acid using an acid-mixed separator, improved conductivity and electrode performance are possible. While not an industry standard, its ease of use has led to its use in purchasing decisions worldwide today. Improving the performance of this algorithmic tester is key to customer satisfaction, and improvements to the acid-mixed separator facilitate these results, as shown in Table 3.

[0091] The following examples detail the analysis of exemplary separators and batteries using computational fluid dynamics (CFD), quantifying the effectiveness of the exemplary embodiments disclosed herein, and reversing, reducing, or completely eliminating stratification in lead-acid batteries, submersible lead-acid batteries, enhanced submersible batteries, or idle-start / stop submersible batteries. The models were generally started in a fully stratified state with high concentrations of acid located in the lower part of the battery and water in the upper part of the battery, with interfaces provided between them.

[0092] A sinusoidal graph of the lateral motion is shown in Figure 17A. This motion may be described as moving the separator and / or battery from a starting position in one direction to a positive 1-foot displacement, reversing the direction to move the separator and / or battery of the model past the starting position to a negative 1-foot displacement, and reversing the direction to move the model back to the starting position. The above motion occurs in 1 second. This motion pattern was used in all CFD models simulating horizontal lateral or horizontal transverse motion and was repeated for the desired time and the number of times required to perform the analysis. The CFD analysis described herein utilized lateral or transverse motion in a direction parallel to the width direction of the exemplary separator. In other words, the motion was horizontal and parallel to the main plane of the exemplary separator.

[0093] In addition, analysis of the CFD model derived the volume homogeneity index (φ) of the acid volume fraction in the liquid electrolyte, where a completely mixed electrolyte has a homogeneity index of 1.0. This value was calculated using Equation 1 below.

[0094]

number

[0095] Figure 17B shows a comparison of a solid rib separator and a serrated rib separator, each subjected to the motion defined in Figure 17A and analyzed using CFD. Both separators analyzed were positive envelope separators. This means that the separator enclosed the positive electrode plate with solid or serrated (and, as described below, segmented) ribs facing the positive electrode plate.

[0096] Figure 18A shows positive enveloped motion after 60 seconds of lateral movement, analyzed using CFD. The solid rib separator is shown, illustrating the mixing of the stratified electrolyte in a submersible lead-acid battery. A small amount of mixing is observed around the outer periphery of the separator, but mixing between the solid ribs is very small, if any. Figure 18B shows the volume uniformity of the analysis, revealing that lateral movement mixing resulted in a 7% increase in volume uniformity.

[0097] Figure 19A shows a positively enveloped serrated rib separator subjected to lateral movement for 60 seconds and analyzed using CFD, illustrating the mixing of the stratified electrolyte in a submersible lead-acid battery. Some mixing is observed on the outer periphery of the separator, and mixing also increases between the inner serrated ribs. Figure 19B shows the volume homogeneity of the analysis, revealing that the mixing from lateral movement resulted in a 12% increase in volume homogeneity.

[0098] Figure 20A shows a comparative analysis of the CFD mixing results of the separators shown in Figures 18A and 19A. Figure 20B shows that the positively enveloped serrated rib separator produces a 5% increase in mixing uniformity compared to the positively enveloped solid rib separator.

[0099] Figure 21 defines the rocking motion used in the CFD analysis of a positively enveloped serrated rib separator. Figure 22 shows the CFD analysis of the visual representation of the serrated rib separator subjected to the rocking motion described in Figure 21.

[0100] Figure 23 is a schematic representation of a separator that includes or encloses (negative envelopes) the negative electrode plate of a submersible lead-acid battery, having solid or serrated (and, as described later, segmented) ribs facing the positive electrode plate.

[0101] Figure 24A is a graphical representation of the CFD analysis of a negatively enveloped serrated rib separator subjected to lateral movement, and is further compared with the graphical representation of the CFD analysis of a positively enveloped serrated rib separator subjected to the same lateral movement. Figure 24B is a graphical representation of the volume uniformity of the negatively enveloped serrated rib separator in Figure 24A, revealing a 22% change in volume uniformity during mixing for 60 seconds from the start of stratification. Figure 24C is a graphical comparison of the volume uniformity of negatively enveloped and positively enveloped serrated rib separators, showing that the negatively enveloped separator has a 10% increase in mixing compared to the positively enveloped separator.

[0102] Turning to Figures 25A–25F, several exemplary embodiments show a segmented rib arrangement with variables that define various segmented rib patterns used in CFD analysis. Figures 26A–26G relate to exemplary embodiments of the present disclosure and show a battery separator having segmented ribs as defined by the patterns in Figures 25A–25F. The exemplary battery separator is shown in Figures 26A–26G, and furthermore, the exemplary battery separator disclosed herein may have any number of columns 2606 1 ~2006 n It may have.

[0103] Figure 27A is a graphical comparison of CFD analyses of a negative-enveloped serrated rib separator and a negative-enveloped split rib separator (as shown in Figure 26D) subjected to substantially lateral or horizontal motion. Figure 27B shows a comparison of volume uniformity of multiple CFD analyses of the previously described separators subjected to lateral motion. The negative-enveloped split rib separator produces a 26% increase in mixing over 60 seconds compared to the negative-enveloped serrated rib separator.

[0104] Moving on to Figure 28A, the figure shows a graphical comparison of CFD analyses of negative-enveloped solid rib separators and negative-enveloped segmented rib separators (as shown in Figure 26D) that have undergone substantially lateral or horizontal motion. Figure 28B shows substantially This shows a comparison of the volume uniformity of multiple CFD analyses of previously described separators subjected to lateral or horizontal movement. The negative enveloped splitting rib separator produces a 28% increase in 60 seconds of mixing.

[0105] Figure 29A details a separator having three divisions of various segmented rib patterns, the divisions changing laterally along the width direction of the separator. It is noted that the divisions may also extend in the longitudinal direction of the separator or both in the longitudinal and width directions of the separator. Furthermore, it is understood that there may be any number of divisions in either or both directions. In addition, the edges of the separator may themselves be divisions so that they are optimized with a clear design and / or ribbed pattern and / or segmented rib pattern, etc., for better results. In certain preferred embodiments herein, the divisions of the separator (for a multi-division separator) are formed so that the mass of the patterning in each division is relatively consistent, and / or the patterned separator extends well on the battery forming equipment, and / or batter formation is accelerated for the effect in acid filling.

[0106] Figure 29B shows the segmented rib pattern variables for a segmented separator. The subscript numbers "1" and "2" correspond to two different segmented rib patterns. In a particular embodiment, segments 1 and 3 (subscript "1") incorporate the same pattern, such as the segmented rib pattern, while segment 2 (subscript "2") has a different pattern, such as the segmented rib pattern, from those of segments 1 and 3. Figure 29C shows the segmented rib variable for a single segmented rib separator.

[0107] Figures 30A to 30H show the separator variables for the three divided rib patterns.

[0108] Figure 31 shows a graphical representation of the CFD analysis of negative envelope separators for four different 3-part divided rib patterns.

[0109] Figure 32A is a graphical comparison of CFD analyses of a negatively enveloped, three-part segmented rib separator and a negatively enveloped, single-part segmented rib separator (as shown in Figure 26D) subjected to lateral movement. Figure 32B shows a comparison of the volume uniformity of acid fractions from multiple CFD analyses of the previously described separators subjected to lateral movement. This graph shows that the three-part segmented separator produces a 1% increase in mixing compared to the single-part segmented separator.

[0110] Figures 33A–33C show the headspace of a battery having splash baffles according to an exemplary embodiment of the present disclosure. These splash baffles may be used in conjunction with any of the exemplary separators described herein. In these embodiments, the headspace of each battery is optimized to further suppress the power or energy (both horizontal and vertical energy) of moving or oscillating electrolyte and / or acid waves or ripples, to further increase the volume uniformity of acid mixing and acid fraction within the lead-acid batter and along all portions of the electrode plates within the battery, approaching or even achieving a volume uniformity of 1.0 (completely mixed). The splash baffles may be formed on or attached to the lid or inner wall of the battery case, or may take the form of devices clipped onto the electrode straps. The splash baffles may further have a planar, curved convex or concave shape, a ridged shape, a sharp or fin-shaped edge, or any other shape. In addition, the electrode straps may be designed or moved to better work with the splash baffle or any other splash and / or movement the electrolyte undergoes while the battery is in motion. The splash baffle may also float on the electrodes or incorporate one or more pivots to optimize the effect of any splash and / or movement the electrolyte undergoes while the battery is in motion.

[0111] Furthermore, the battery design may be modified to help facilitate stratification. One such example may involve mounting the battery on an elastic mount, such as a spring, or rubber or other viscoelastic material, allowing the battery to continue moving or vibrating after a change in velocity. The battery case may be made longer, with more electrolyte added to increase the overall head pressure of the electrolyte supply within the battery. The battery may also be designed as a horizontal cylinder, an egg shape, or even a sphere. In addition, the case lid may be designed as a hemisphere.

[0112] Figures 34A–34I illustrate various details of the exemplary embodiments of this disclosure.

[0113] Figure 35 shows a separator for a long cell battery having a rib pattern substantially as shown in Figure 26D. Figure 36 shows the volume uniformity over time, derived from the CFD analysis of the separator shown in Figure 35, compared to other separator designs. The test cell was simulated to have undergone lateral movement as shown in Figure 17A. The separator was parallel to the direction of movement for 60 seconds. The thin lower line represents a short separator with a solid rib pattern, and the thick lower line represents a long separator with a solid rib design. The thin upper line represents a short separator with a preferred segmented rib pattern, and the thick upper line represents a long separator with a preferred segmented rib pattern. As shown in the figure, the short separator with a solid rib pattern showed a 13% increase in its volume uniformity compared to the long separator with a solid rib pattern, which showed only a 7% increase. The short separator with a preferred segmented rib pattern showed a 28% increase in its volume uniformity. Long separators with a suitable segmented rib pattern showed a 62% increase in their volume uniformity through 60 seconds of lateral movement, the largest increase among the lots inspected.

[0114] Figure 37 shows a comparison of the velocity contour time history between the Concept 1 Tol acid mixed contour of the invention and the conventional solid baffled Tol contour.

[0115] Figure 38 shows a spacer of an exemplary invention having a pattern of segmented ribs placed between a separator and an electrode. As shown in the figure, the segmented ribs are held in place by a mesh of thin stringers. The stringers are shown in vertical and horizontal arrangements, but it is understood that other angles may be incorporated.

[0116] Figures 39A to 39C illustrate exemplary embodiments of dimensional values ​​showing the contour, spacing, and headspace of the power-type separator of the invention in, for example, a long battery or battery case.

[0117] Figures 40 and 41 show the contour prototype of the acid mixture contour of the exemplary invention.

[0118] Figure 42 includes an image demonstrating the mixed advantage of the invention's contour compared to the contour of conventional solid ribs.

[0119] Furthermore, the battery design may be modified to help facilitate stratification. One such example may involve mounting the battery on an elastic mount, such as a spring, or rubber or other viscoelastic material, allowing the battery to continue moving or vibrating after a change in velocity. The battery case may be made longer, with more electrolyte added to increase the overall head pressure of the electrolyte supply within the battery. The battery may also be designed as a horizontal cylinder, an egg shape, or even a sphere. In addition, the case lid may be designed as a hemisphere.

[0120] The separators described herein are further, for example, weirs, immersion tubes, and acid pumps. It may be used in conjunction with other devices used for stratification prevention / reversal, such as a bubbler, displacement device, or any combination thereof. Several such devices are disclosed below: U.S. Patent Application Publication Nos. 2012 / 0214032 (Franklin, et al.), 2004 / 0067410 (Jones), and 2003 / 0148170 (Jones), and U.S. Patent Nos. 6274263 (Jones), 4629622 (Yonezu, et al.), and 4565748 (Dahl). All of these are incorporated herein by reference. The separator may be in the form of a leaf, an envelope, or a complete tube / sleeve. The separator may further comprise a full-contour pleat / seal or a discontinuous pleat / seal, and may further comprise an opening at the fold at the bottom of the folded separator.

[0121] It is understood that any of the rib patterns described herein have spacing between rows and can increase gas during overcharging events. Furthermore, a segmented rib pattern may have no longitudinal spacing between rows of segmented ribs and provide strength when the separator is folded to form an envelope. In addition, the segmented rib separator may be further embossed. It is further understood that either the rib pattern or other protrusions may be provided on any internal surface of the battery case or on any surface of either or both of the positive and negative electrodes. With respect to batteries installed in a vehicle, a preferred embodiment may position the separator generally parallel to the movement of the vehicle in order to take advantage of the vehicle's starting and stopping movements.

[0122] The improved separators described herein, such as the segmented rib separators described herein, may further help prevent the formation of sulfated crystals and may also help to provide a more uniform thermal distribution and / or thermal mixing and / or thermal dissipation or heat release (heat release in less time than known separators, such as solid rib separators for immersion lead-acid batteries). The exemplary segmented rib separators described herein may also provide improved, faster, or more efficient filling of immersion lead-acid batteries, gel batteries, and / or reinforced immersion batteries.

[0123] In various embodiments of this disclosure, the disclosed separator reduces stratification, or even results in complete removal of stratification, by causing the mixing level or volume uniformity of the acid or electrolyte in a submersible lead-acid battery to approach 1.0 or nearly 1.0. In various embodiments, the separator disclosed herein is also a low electrical resistance (ER) separator. In such embodiments, the separator may include improvements such as improved fillers that increase porosity, pore size, internal pore surface area, wettability and / or the surface area of ​​the separator. In some embodiments, the improved fillers have a higher structural configuration and / or smaller particle size and / or a different amount of silanol groups than fillers known to date, and / or are more hydroxylated than fillers known to date. The improved fillers may absorb more oil and / or allow for the incorporation of a larger amount of process oil during separator formation without simultaneous shrinkage or compression when the oil is removed after extrusion. For example, the improved separator is formed using silica having an intrinsic oil absorption value of approximately 175-350 ml / 100g, 200-350 ml / 100g depending on the embodiment, 250-350 ml / 100g depending on the embodiment, and in some embodiments, 260-320 ml / 100g, although other oil absorption values ​​are also possible.

[0124] The filler may further reduce the so-called hydration spheres of electrolyte ions and enhance membrane permeation transport of electrolyte ions, thereby further lowering the overall electrical resistance or ER of the battery, such as in an enhanced immersion battery or system.

[0125] The filler material or multiple fillers promote the flow of electrolytes and ions across the separator (gold It may include various species (such as polar species of a genera). Furthermore, such a feature reduces the overall electrical resistance, making such a separator usable in submersible batteries such as reinforced submersible batteries.

[0126] The low-ER microporous separators described herein may further comprise novel and improved pore morphologies and / or novel and improved filament morphologies such that when the separator is used in a submersible lead-acid battery, such separators contribute to a significant reduction in electrical resistance in such submersible lead-acid batteries. Such improved pore morphologies and / or filament morphologies may result in separators in which the pores and / or filaments are close to a shish kebab (or shish kebab) type morphology. Another way to describe the novel and improved pore shapes and structures is a rough filament morphology in which silica nodes or silica nodes are present in the kebab-type configuration of polymer filaments (which are sometimes called shish) within the battery separator. Furthermore, in certain embodiments, the silica structure and pore structure of the separator according to the present invention may be described as a skeletal structure, vertebral structure, or spinal cord structure, and the silica nodes in the polymer kebab along the polymer protofiber may appear like vertebrae or discs ("kebabs") and be oriented perpendicular to the elongated central vertebra or protofiber (extended chain polymer crystals), substantially close to a spinal column shape ("shish").

[0127] In some cases, an improved battery having an improved separator having an improved pore morphology and / or filamentous morphology may exhibit a 20% reduction in electrical resistance, in some cases a 25% reduction, in some cases a 30% reduction, and in some cases a greater than 30% drop in electrical resistance ("ER") (which reduces the internal resistance of the battery). On the other hand, such a separator maintains and preserves the balance of other key, desirable mechanical properties of lead-acid battery separators. Furthermore, in certain embodiments, the separators described herein have novel and / or improved pore morphologies to allow more electrolyte to flow through or fill the pores and / or voids compared to known separators. The ultra-high molecular weight polyethylene in the separator may comprise a polymer with a shish-kebab configuration comprising a plurality of elongated chain crystals (shishi configuration) and a plurality of folded chain crystals (kebab configuration), wherein the average frequency or periodicity of the kebab configuration is 1 nm to 150 nm, preferably 10 nm to 120 nm, and more preferably 20 nm to 100 nm (at least in the rib-side portion of the separator). In some of these low-ER embodiments of the separator, the lead-acid battery separator described herein comprises a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica, wherein the molecular ratio of OH groups to Si groups in the filler is 29 The values ​​are measured by Si-NMR and are in the range of 21:100 to 35:100, in some embodiments, 23:100 to 31:100, in some embodiments, 25:100 to 29:100, and in certain preferred embodiments, 27:100 or higher.

[0128] In certain selected embodiments, the disclosed separator has an electrical resistance, for example, about 200 mΩcm. 2 , 180 mΩcm 2 , 160 mΩcm 2 , 140 mΩcm 2 , 120 mΩcm 2 , 100 mΩcm 2 , 80 mΩcm 2 , 60 mΩcm 2 , 50 mΩcm2 , 40 mΩcm 2 , 30 mΩcm 2 , or 20 mΩcm 2 It exhibits a reduction in electrical resistance of approximately the same magnitude. In various embodiments, the separators described herein exhibit a reduction in ER of about 20% or more compared to known separators of the same thickness. For example, a known separator has an ER of 60 mΩcm. 2 It may have an ER value of the same thickness. The light separator has an impedance of approximately 48 mΩcm. 2 It has an ER value of less than . It has a low ER in this specification. The separator described herein may have any or all of the characteristics described in U.S. Provisional Patent Application No. 62 / 319959, owned by Dalamic Corporation and filed on April 8, 2016, which is thus incorporated by reference in its entirety.

[0129] In at least selected embodiments, this disclosure covers improved lead-acid batteries, improved systems including lead-acid batteries, and / or battery separators, improved vehicles including such systems, methods of manufacture or use, or combinations thereof, such as submersible lead-acid batteries. In at least specific embodiments, this disclosure covers improved submersible lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacture, inspection or use, or combinations thereof, such improved submersible lead-acid batteries. In addition, this specification discloses methods, systems, batteries, and / or battery separators for reducing stratification in submersible lead-acid batteries and extending battery life and performance.

[0130] Exemplary separators, such as those disclosed herein, may preferably be characterized by having or providing conductivity that improves over time. Conductivity may be determined, for example, as cold cranking amperes (CCA) measured with a Midtronics tester. For example, a lead-acid battery equipped with the separator of the invention may show a decrease in CCA of less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% over 30 days as measured by a Midtronics CCA tester.

[0131] The separator of the present invention preferably comprises a porous membrane (such as a microporous membrane having pores of less than about 1 micron, a mesoporous membrane, or a macroporous membrane having pores larger than about 1 micron) made of natural or synthetic materials such as polyolefins, polyethylene, polypropylene, phenolic resins, PVC, rubber, synthetic pulp (SWP), glass fibers, cellulosic fibers, or combinations thereof, more preferably a microporous membrane made of a thermoplastic polymer. A suitable microporous membrane may have a pore diameter of about 0.1 microns (100 nanometers) and a porosity of about 60%. The thermoplastic polymer may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead-acid batteries. Suitable thermoplastic polymers include polyvinyl and polyolefin. Polyvinyl includes, for example, polyvinyl chloride (PVC). Polyolefins include, for example, polyethylene such as ultra-high molecular weight polyethylene (UHMWPE) and polypropylene. A suitable embodiment may include a mixture of a filler (e.g., silica) and UHMWPE.

[0132] The porous membrane layer may include polypropylene, ethylene-butene copolymer, and preferably polyethylene, more preferably high molecular weight polyethylene (e.g., polyethylene having a molecular weight of at least 600,000), even more preferably ultra-high molecular weight polyethylene (e.g., polyolefins such as polyethylene having a molecular weight of at least 1,000,000, particularly more than 4,000,000, and most preferably 5,000,000 to 8,000,000 (measured by viscosity measurement and calculated by Margolies' equation), a standard load melt index of substantially 0 (as specified and measured in ASTM D1238 (condition E) using a standard load of 2,160 g), and a viscosity number of 600 ml / g or more, preferably 1,000 ml / g or more, more preferably 2,000 ml / g or more, and most preferably 3,000 ml / g or more (determined with a solution of 0.02 g of polyolefin in 100 g of decalin at 130°C).

[0133] According to at least one embodiment, the porous membrane may include ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil and precipitated silica. According to at least one embodiment, the microporous membrane may include ultra-high molecular weight polyethylene (UHMWPE) mixed with process oil, additives and precipitated silica. The mixture may also contain small amounts of other additives or agents, such as those common in separator technology (e.g., wetting agents, colorants, antistatic agents, and / or similar). In some cases, the microporous polymer layer may be a homogeneous mixture of 8-100 volume% polyolefin, 0-40 volume% plasticizer, and 0-92 volume% inert filler. The filler may be dry, finely fragmented silica. A preferred plasticizer is petroleum. The plasticizer is helpful in imparting porosity to the battery separator because it is the most easily removed component from the polymer-filler-plasticizer mixture.

[0134] In some embodiments, the porous membrane may be produced in an extruder by mixing about 30% by weight silica with about 10% by weight UHMWPE and about 60% process oil. The microporous membrane can be produced by passing the raw material through a heated extruder, passing the extruded material through a mold and placing it in a nip formed by two heated calender rolls to form a continuous web, extracting a considerable amount of process oil from the web using a solvent, drying the extracted web, cutting the web into strips of a predetermined width to form lanes, and winding the lanes to form a roll. Various groove patterns may be engraved on the calender rolls to impart ribs, serrations, embossing, etc., to the membrane. Alternatively, or further, ribs, etc., may be imparted to the porous membrane by passing the extruded membrane through additional appropriately grooved calender rolls or a press.

[0135] Porous membranes can be equipped with additives, surfactants, agents, fillers, or a combination of additives in various ways. For example, the additive or a combination of additives may be coated onto the porous membrane when added to a mixture used to form the completed and / or membrane (e.g., after extraction). According to a preferred embodiment, the additive or a solution of additives is coated onto the surface of the porous membrane. This variant is particularly suitable for coating non-thermally stable additives and additives that are easily soluble in solvents used for subsequent extraction. Particularly suitable solvents for the additives according to the present invention are low molecular weight alcohols such as methanol and ethanol, as well as mixtures of these alcohols with water. Coating may be applied to the side of the microporous membrane facing the negative electrode, the side facing the positive electrode, or both sides.

[0136] The coating may also be carried out by immersing the microporous membrane in the additive or a solution of the additive, followed optionally by removing the solvent, for example, by drying. In this way, the coating of the additive can be combined with extraction, which is often performed, for example, during separator manufacturing.

[0137] Other suitable options include mixing one or more additives with a mixture of a thermoplastic polymer and optionally other additives used to create fillers and porous membranes. The additive-containing homogeneous mixture is then formed into a web-like material.

[0138] The separator of the present invention may be a low-ER separator, a low-moisture-loss separator, and / or has portions including at least protrusions, segmented ribs, serrated ribs, discontinuous ribs, and / or equivalents (but not solid ribs) that can improve the acid mixing or conductivity of the separator. Protrusions include characteristics such as short rib portions, lumps, embossing, etc. Protrusions may be present on either face or both faces of the separator. Typically, protrusions are present on at least the side facing the positive electrode plate (positive electrode active material or PAM). Protrusions may be arranged in the row direction, with protrusions in each row spaced apart from each other and from protrusions in adjacent rows. In some cases, protrusions may be located on the side of the separator facing the positive electrode active material, on the side of the separator facing the negative electrode active material (or NAM), or on both sides of the separator.

[0139] In some embodiments of the present invention, the projection is a rib having a rib height of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, or 1.5 mm.

[0140] Depending on the embodiment of the present invention, the projections are at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, and 0.3 mm. These are short ribs having a rib width of 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, or 1.5 mm. The ribs can have widths between approximately 0.005-1.5 mm, 0.01-1.0 mm, 0.025-1.0 mm, 0.05-1.0 mm, 0.075-1.0 mm, 0.1-1.0 mm, 0.2-1.0 mm, 0.3-1.0 mm, 0.4-1.0 mm, 0.5-1.0 mm, 0.4-0.8 mm, or 0.4-0.6 mm.

[0141] The separator may include negative longitudinal or transverse ribs or mini-ribs, such as negative ribs having a height of about 25 to 250 microns, probably preferably about 50 to 125 microns, and more preferably about 75 microns.

[0142] In certain embodiments, the projection may include ribs, each rib having a longitudinal axis positioned at an angle between 0° and less than 180° with respect to the upper end of the separator. In some cases, all ribs of the separator may be positioned at the same angle. On the other hand, in other embodiments, the ribs may be positioned at different angles. For example, in some embodiments, the separator may include several rows of ribs, with at least some of the rows having ribs at an angle Θ with respect to the upper end of the separator. All ribs in a single row may have the same approximate angle, but in other cases, a single row may include ribs at different angles.

[0143] In certain cases, the entire surface of the separator includes several rows of protrusions, while in other embodiments, certain segments of the separator's surface do not include protrusions. These segments may be located along any edge of the separator, including the top, bottom, or sides, or they may be located toward the center of the separator. The segments are located around one or more surfaces that have portions with protrusions.

[0144] In certain preferred embodiments having segmented ribs (see Figure 1), the portion has at least two sets of rows, the ribs of the first row are arranged at angles from 0° to less than 180°, and the ribs of the second row are arranged at angles from 0° to less than 180°, but may be the same as or different from the angles of the ribs of the first set. Figure 40 includes a depiction of a separator (100) including an upper end (101) having sets of first (102) and second (103) rows.

[0145] In certain other preferred embodiments (see Figure 41), the second portion has at least two sets of rows, the ribs of the first row are arranged at angles from 0° to less than 180°, and the ribs of the second row are arranged at angles from 0° to less than 180°, but may be the same as or different from the angles of the ribs of the first set of rows. Figure 41 includes a depiction of a separator (400) including an upper end (401) having a central first portion (402) and an outer second (403) portion.

[0146] In some cases, the second part is referred to as R in this specification. 5 (404) specified, backway Θ relative to the upper end of B 5 It includes a fifth set of rows having ribs with an angle (405). Θ 5 These ranges from 0° to 90°, 30° to 85°, 45° to 85°, 60° to 85°, 60° to 80°, or 60° to 75°. Θ 5 A preferred value is 90°. The part is referred to as R in this specification. 6 (406) is specified, Θ 6 It has an angle (407) and an angle Θ with respect to the upper end of the back web. 6 It may include a sixth set of rows having ribs. Θ 6 These ranges from 90° to less than 180°, 95° to 150°, 95° to 120°, 100° to 120°, or 105° to 120°. Θ 6 The preferred value is 90°. The ribs of different rows are as shown in (400). They may have the same or different dimensions. The distance between adjacent rows may be -5 to 5 mm. Negative numbers indicate the degree of row overlap. The distance can be measured from central rib to central rib.

[0147] If different lines exist, the lines may exist in a repeating pattern. The simplest repeating pattern -R 5 -R 6 - may be seen at (400). For other patterns, - R 5 -R 5 -R 6 -,-R 5 -R 5 -R 5 -R 6 -,-R 5 -R 5 -R 6 -R 6 -,-R 5 -R 5 -R 5 -R 5 -R 6 -,-R 6 -R 5 -R 5 -R 5 -R 6 -,-R 5 -R 5 -R 5 -R 6 -R 6 - etc. are included.

[0148] In some selected embodiments, the porous separator may have negative longitudinal or transverse ribs as protrusions on the opposite side of the membrane. The negative or back ribs may be parallel to the upper end of the separator, or positioned obliquely thereto. For example, the transverse ribs may be oriented at approximately 90°, 80°, 75°, 60°, 50°, 45°, 35°, 25°, 15°, or 5° relative to the upper end. The transverse ribs may be oriented at approximately 90–60°, 60–30°, 60–45°, 45–30°, or 30–0° relative to the upper end. Typically, the transverse ribs are located on the membrane surface facing the negative electrode. In some embodiments of the present invention, the ribbed membrane may have transverse rib heights of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the present invention, the ribbed membrane may have transverse rib heights of approximately 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0149] In some embodiments of the present invention, the ribbed membrane may have transverse rib widths of at least about 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. In some embodiments of the present invention, the ribbed membrane may have transverse rib widths of approximately 1.0 mm, 0.5 mm, 0.25 mm, 0.20 mm, 0.15 mm, 0.10 mm, or 0.05 mm.

[0150] In certain selected embodiments, the porous membrane may have transverse rib heights of about 0.10 to 0.15 mm and longitudinal rib heights of about 0.1 to 0.15 mm. Depending on the embodiment, the porous membrane may have transverse rib heights of about 0.10 to 0.125 mm and longitudinal rib heights of about 0.1 to 0.125 mm.

[0151] The microporous membrane may have a back web thickness of at least 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm. The ribbed separator may have a back web thickness of about 1.0 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, or 0.1 mm or less. Depending on the embodiment, the microporous membrane may have a back web thickness between about 0.1 and 1.0 mm, 0.1 and 0.8 mm, 0.1 and 0.5 mm, 0.1 and 0.5 mm, 0.1 and 0.4 mm, or 0.1 and 0.3 mm. Depending on the embodiment, the microporous membrane may have a back web thickness of about 0.2 mm.

[0152] The separator of the present invention may be provided in the form of a sheet or in the form of a wrap, sleeve, pocket, or envelope. Depending on the embodiment, a microporous membrane covered with at least one fiber layer on at least one surface is provided as a pocket or envelope. When a fiber layer is present, it is preferable that the microporous membrane has a larger surface area than the fiber layer. Therefore, when joining the microporous membrane and the fiber layer, the fiber layer does not completely cover the microporous layer. It is preferable that at least two opposing edge regions of the membrane layer are left uncovered, providing edges for heat sealing to facilitate the formation of the pocket or envelope. The separator may be processed to form a hybrid envelope. A hybrid envelope can be created by folding a separator sheet in half to form an envelope and creating one or more cuts or openings before, during, or after joining the edges of the separator sheets together. The two sides are joined together using welding or mechanical sealing to form a seam that brings one side of the separator sheet into contact with the other side of the separator sheet. Welding can be performed, for example, using heat or ultrasonic treatment. As a result of this process, the shape becomes an envelope with a folded edge at the bottom and two lateral edges.

[0153] Separators disclosed herein in the form of envelopes may have one or more slits or openings along the folded or sealed folds of the envelope. The length of the openings may be at least 1 / 50, 1 / 25, 1 / 20, 1 / 15, 1 / 10, 1 / 8, 1 / 5, 1 / 4, or 1 / 3 of the length of all edges. The length of the openings may be 1 / 50 to 1 / 3, 1 / 25 to 1 / 3, 1 / 20 to 1 / 3, 1 / 20 to 1 / 4, 1 / 15 to 1 / 4, 1 / 15 to 1 / 5, or 1 / 10 to 1 / 5 of the length of all edges. Hybrid envelopes may have 1 to 5, 1 to 4, 2 to 4, 2 to 3, or 2 openings, which may or may not be evenly distributed along the length of the lower end. It is preferable that there are no openings at the corners of the envelope. The cuts may be made after the separator has been folded and sealed to form an envelope, or they may be formed prior to shaping the porous membrane into an envelope.

[0154] Separators as disclosed herein may be characterized by improved conductivity over time. Conductivity may be determined, for example, as cold cranking amperes (CCA) measured with a Midtronics tester. For example, a lead-acid battery equipped with the separator of the present invention may show a decrease in CCA of less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% over 30 days as measured by a Midtronics CCA tester. In contrast, the decrease in CCA observed in conventional batteries under similar conditions is often greater.

[0155] The separators provided herein enable the manufacture of batteries with reduced moisture loss and stray current compared to batteries consisting of conventional separators. Depending on the embodiment, moisture loss may be reduced by more than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. Depending on the embodiment, stray current may be reduced by more than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. Batteries prepared using the disclosed separators showed a decrease in internal resistance over time, and in some cases, no increase in internal resistance at all.

[0156] In addition to reducing moisture loss and extending battery life, suitable separators are designed to offer other advantages. Regarding assembly, the separators have negative transverse ribs intended to maximize bending stiffness and achieve the highest manufacturing productivity. To prevent short circuits during and after rapid assembly, the separators have superior puncture and oxidation resistance compared to standard PE separators.

[0157] In at least selected embodiments, the Disclosure or Invention covers improved battery separators, low-ER or high-conductivity separators, improved lead-acid batteries such as immersion lead-acid batteries or high-conductivity batteries, and / or improved vehicles including such batteries, and / or methods for manufacturing or using such separators or batteries, and / or combinations thereof. In at least specific embodiments, the Disclosure or Invention covers improved lead-acid batteries incorporating improved separators and exhibiting increased conductivity.

[0158] The improved separators described herein, such as the segmented rib separators described herein, may further help prevent the formation of sulfated crystals and may also help to provide a more uniform thermal distribution and / or thermal mixing and / or thermal dissipation or heat release (heat release in less time than known separators, such as solid rib separators for immersion lead-acid batteries). The exemplary segmented rib separators described herein may also provide improved, faster, or more efficient filling of immersion lead-acid batteries, gel batteries, and / or reinforced immersion batteries.

[0159] In various embodiments of this disclosure, the disclosed separator reduces stratification, or even results in complete removal of stratification, by causing the mixing level or volume uniformity of the acid or electrolyte in a submersible lead-acid battery to approach 1.0 or nearly 1.0. In various embodiments, the separator disclosed herein is also a low electrical resistance (ER) separator. In such embodiments, the separator may include improvements such as improved fillers that increase porosity, pore size, internal pore surface area, wettability and / or the surface area of ​​the separator. In some embodiments, the improved fillers have a higher structural configuration and / or smaller particle size and / or a different amount of silanol groups than fillers known to date, and / or are more hydroxylated than fillers known to date. The improved fillers may absorb more oil and / or allow for the incorporation of a larger amount of process oil during separator formation without simultaneous shrinkage or compression when the oil is removed after extrusion. For example, the improved separator is formed using silica having an intrinsic oil absorption value of approximately 175-350 ml / 100g, 200-350 ml / 100g depending on the embodiment, 250-350 ml / 100g depending on the embodiment, and in some embodiments, 260-320 ml / 100g, although other oil absorption values ​​are also possible.

[0160] The filler may further reduce the so-called hydration layer of electrolyte ions and enhance membrane permeation transport of electrolyte ions, thereby further lowering the overall electrical resistance or ER of the battery, such as in a reinforced immersion battery or system.

[0161] The filler material or a combination of fillers may contain various types (such as polar species of metals) that promote the flow of electrolytes and ions across the separator. Furthermore, such a material reduces the overall electrical resistance, allowing such a separator to be used in immersion batteries, such as enhanced immersion batteries.

[0162] The low-ER microporous separators described herein may further comprise novel and improved pore morphologies and / or novel and improved filament morphologies such that when the separator is used in a submersible lead-acid battery, such separators contribute to a significant reduction in electrical resistance in such submersible lead-acid batteries. Such improved pore morphologies and / or filament morphologies may result in separators in which the pores and / or filaments are close to a shish kebab (or shish kebab) type morphology. Another way to describe the novel and improved pore shapes and structures is a rough filament morphology in which silica nodes or silica nodes are present in the kebab-type configuration of polymer filaments (which are sometimes called shish) within the battery separator. Furthermore, in certain embodiments, the silica structure and pore structure of the separator according to the present invention may be described as a skeletal structure, vertebral structure, or spinal cord structure, and the silica nodes in the polymer kebab along the polymer protofiber may appear like vertebrae or discs ("kebabs") and be oriented perpendicular to the elongated central vertebra or protofiber (extended chain polymer crystals), substantially close to a spinal column shape ("shish").

[0163] In some cases, an improved battery having an improved separator having an improved pore morphology and / or filamentous morphology may exhibit a 20% reduction in electrical resistance, in some cases a 25% reduction, in some cases a 30% reduction, and in some cases a greater than 30% drop in electrical resistance ("ER") (which reduces the internal resistance of the battery). On the other hand, such a separator maintains and preserves the balance of other key, desirable mechanical properties of lead-acid battery separators. Furthermore, in certain embodiments, the separators described herein have novel and / or improved pore morphologies to allow more electrolyte to flow through or fill the pores and / or voids compared to known separators. The ultra-high molecular weight polyethylene in the separator may comprise a polymer with a shish-kebab configuration comprising a plurality of elongated chain crystals (shishi configuration) and a plurality of folded chain crystals (kebab configuration), wherein the average frequency or periodicity of the kebab configuration is 1 nm to 150 nm, preferably 10 nm to 120 nm, and more preferably 20 nm to 100 nm (at least in the rib-side portion of the separator). In some of these low-ER embodiments of the separator, the lead-acid battery separator described herein comprises a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica, wherein the molecular ratio of OH groups to Si groups in the filler is 29 The values ​​are measured by Si-NMR and are in the range of 21:100 to 35:100, in some embodiments, 23:100 to 31:100, in some embodiments, 25:100 to 29:100, and in certain preferred embodiments, 27:100 or higher.

[0164] In certain selected embodiments, the disclosed separator has an electrical resistance, for example, about 200 mΩcm. 2 , 180 mΩcm 2 , 160 mΩcm 2 , 140 mΩcm 2 , 120 mΩcm 2 , 100 mΩcm 2 , 80 mΩcm 2 , 60 mΩcm 2 , 50 mΩcm2 , 40 mΩcm 2 , 30 mΩcm 2 , or 20 mΩcm 2 It exhibits a reduction in electrical resistance of approximately the same magnitude. In various embodiments, the separators described herein exhibit a reduction in ER of about 20% or more compared to known separators of the same thickness. For example, a known separator has an ER of 60 mΩcm. 2 It may have an ER value of approximately 48 mΩcm. Furthermore, the separator according to the present invention at the same thickness has an ER value of approximately 48 mΩcm. 2 Having an ER value of less than . Separators having a low ER as described herein may have any or all of the characteristics described in U.S. Provisional Patent Application No. 62 / 319959, owned by Dalamic Corporation and filed on April 8, 2016, which is thus incorporated by reference in its entirety.

[0165] In at least selected embodiments, this disclosure covers improved lead-acid batteries, improved systems including lead-acid batteries, and / or battery separators, improved vehicles including such systems, methods of manufacture or use, or combinations thereof, such as submersible lead-acid batteries. In at least specific embodiments, this disclosure covers improved submersible lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacture, inspection or use, or combinations thereof, such improved submersible lead-acid batteries. In addition, this specification discloses methods, systems, batteries, and / or battery separators for reducing stratification in submersible lead-acid batteries and extending battery life and performance.

[0166] In various embodiments of this disclosure, the disclosed separator reduces stratification, or even results in complete removal of stratification, by causing the mixing level or volume uniformity of the acid or electrolyte in a submersible lead-acid battery to approach 1.0 or nearly 1.0. In various embodiments, the separator disclosed herein is also a low electrical resistance (ER) separator. In such embodiments, the separator may include improvements such as improved fillers that increase porosity, pore size, internal pore surface area, wettability and / or the surface area of ​​the separator. In some embodiments, the improved fillers have a higher structural configuration and / or smaller particle size and / or a different amount of silanol groups than fillers known to date, and / or are more hydroxylated than fillers known to date. The improved fillers may absorb more oil and / or allow for the incorporation of a larger amount of process oil during separator formation without simultaneous shrinkage or compression when the oil is removed after extrusion. For example, the improved separator is formed using silica having an intrinsic oil absorption value of approximately 175-350 ml / 100g, 200-350 ml / 100g depending on the embodiment, 250-350 ml / 100g depending on the embodiment, and in some embodiments, 260-320 ml / 100g, although other oil absorption values ​​are also possible.

[0167] The filler may further reduce the so-called hydration layer of electrolyte ions and enhance membrane permeation transport of electrolyte ions, thereby further lowering the overall electrical resistance or ER of the battery, such as in a reinforced immersion battery or system.

[0168] The filler material or a combination of fillers may contain various types (such as polar species of metals) that promote the flow of electrolytes and ions across the separator. Furthermore, such a material reduces the overall electrical resistance, allowing such a separator to be used in immersion batteries, such as enhanced immersion batteries.

[0169] The low-ER microporous separators described herein may further comprise novel and improved pore morphologies and / or novel and improved filament morphologies such that when the separator is used in a submersible lead-acid battery, such separators contribute to a significant reduction in electrical resistance in such submersible lead-acid batteries. Such improved pore morphologies and / or filament morphologies may result in separators in which the pores and / or filaments are close to a shish kebab (or shish kebab) type morphology. Another way to describe the novel and improved pore shapes and structures is a rough filament morphology in which silica nodes or silica nodes are present in the kebab-type configuration of polymer filaments (which are sometimes called shish) within the battery separator. Furthermore, in certain embodiments, the silica structure and pore structure of the separator according to the present invention may be described as a skeletal structure, vertebral structure, or spinal cord structure, and the silica nodes in the polymer kebab along the polymer protofiber may appear like vertebrae or discs ("kebabs") and be oriented perpendicular to the elongated central vertebra or protofiber (extended chain polymer crystals), substantially close to a spinal column shape ("shish").

[0170] In some cases, an improved battery having an improved separator having an improved pore morphology and / or filamentous morphology may exhibit a 20% reduction in electrical resistance, in some cases a 25% reduction, in some cases a 30% reduction, and in some cases a greater than 30% drop in electrical resistance ("ER") (which reduces the internal resistance of the battery). On the other hand, such a separator maintains and preserves the balance of other key, desirable mechanical properties of lead-acid battery separators. Furthermore, in certain embodiments, the separators described herein have novel and / or improved pore morphologies to allow more electrolyte to flow through or fill the pores and / or voids compared to known separators. The ultra-high molecular weight polyethylene in the separator may comprise a polymer with a shish-kebab configuration comprising a plurality of elongated chain crystals (shishi configuration) and a plurality of folded chain crystals (kebab configuration), wherein the average frequency or periodicity of the kebab configuration is 1 nm to 150 nm, preferably 10 nm to 120 nm, and more preferably 20 nm to 100 nm (at least in the rib-side portion of the separator). In some of these low-ER embodiments of the separator, the lead-acid battery separator described herein comprises a filler selected from the group consisting of silica, precipitated silica, fumed silica, and precipitated amorphous silica, wherein the molecular ratio of OH groups to Si groups in the filler is 29 The values ​​are measured by Si-NMR and are in the range of 21:100 to 35:100, in some embodiments, 23:100 to 31:100, in some embodiments, 25:100 to 29:100, and in certain preferred embodiments, 27:100 or higher.

[0171] In certain selected embodiments, the disclosed separator has an electrical resistance, for example, about 200 mΩcm. 2 , 180 mΩcm 2 , 160 mΩcm 2 , 140 mΩcm 2 , 120 mΩcm 2 , 100 mΩcm 2 , 80 mΩcm 2 , 60 mΩcm 2 , 50 mΩcm2 , 40 mΩcm 2 , 30 mΩcm 2 , or a reduction in electrical resistance of about the same magnitude as 20 mΩcm 2 shows. In various embodiments, the separator described herein shows a reduction in ER of about 20% or more compared to known separators of the same thickness. For example, a known separator may have an ER value of 60 mΩcm 2 . And the separator according to the present invention at the same thickness has an ER value of less than about 48 mΩcm 2 . The separator described herein having a low ER is owned by DARAMIC and may have any or all of the characteristics described in U.S. Provisional Patent Application No. 62 / 319959, filed on April 8, 2016, which provisional application is hereby incorporated by reference in its entirety.

[0172] At least according to selected embodiments, the present disclosure is directed to improved lead-acid batteries, such as flooded lead-acid batteries, improved systems including lead-acid batteries, and / or battery separators, improved battery separators, improved vehicles including such systems, manufacturing or use methods, or combinations thereof. At least according to certain embodiments, the present disclosure is directed to improved flooded lead-acid batteries, improved battery separators for such batteries, and / or methods of manufacturing, inspecting, or using such improved flooded lead-acid batteries, or combinations thereof. Additionally, methods, systems, batteries, and / or battery separators for reducing stratification in flooded lead-acid batteries and extending battery life and performance are disclosed herein.

[0173] Depending on the embodiment, the improved highly conductive separator may be a low-ER separator, a low water loss separator, a segmented or serrated rib separator, and / or may optionally include a coating on one or both sides. Such a coating may include a surfactant or other materials. Depending on the embodiment, the coating may include, for example, one or more materials described in U.S. Patent Publication No. 2012 / 0094183, which is incorporated herein by reference. Such a coating may, for example, reduce the overcharge voltage of the battery system, thereby reducing grid corrosion, extending battery life, and preventing drying out and / or water loss.

[0174] The separators utilized in various embodiments herein may include one or more additives. This may be because such additives may strengthen the separator for a particular stop / start flooded lead-acid battery for a particular vehicle. One such additive present in polyolefins is a surfactant. On the other hand, other such additives may include one or more latex additives. Suitable surfactants include surfactants such as alkyl sulfates, alkyl aryl sulfonate salts, alkylphenol-alkylene oxide adducts, soaps, alkyl naphthalene sulfonates, dialkyl esters of sulfosuccinates, quaternary amines, block copolymers of ethylene oxide and propylene oxide, and salts of mono and dialkyl phosphate esters. The additives can be nonionic surfactants such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated fatty alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicon-based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphate esters, and sucrose fatty acid esters.

[0175] The preceding descriptions of the structure and method are presented for illustrative purposes only. Examples disclose exemplary embodiments, including best modes, and are used to enable any person skilled in the art to carry out the invention, including constructing and using any apparatus or system and performing any incorporated method. These examples are not intended to be exhaustive or to limit the invention to the detailed steps and / or forms disclosed. Numerous modifications and variations are possible from the viewpoint of the above teachings. The characteristics described herein may be combined in any combination. The steps of the method described herein may be carried out in any physically possible sequence. The patentable scope of the invention is defined by the appended claims and may include other examples that a person skilled in the art can conceive. Such other examples may have structural elements that are no different from the wording of the claims, or equivalents that have only minor differences from the wording of the claims. If it includes structural elements, it is intended to be within the scope of the claim.

[0176] The compositions and methods of the appended claims are not limited to the scope of application of the specific compositions and methods described herein, and the specific compositions and methods described herein are intended to describe only a few aspects of the claims. Any functionally equivalent compositions and methods are intended to be within the scope of the claims. In addition to those shown and described herein, various variations of compositions and methods are intended to be within the scope of the appended claims. Furthermore, although only specific representative compositions and method steps disclosed herein are specifically described, other combinations of compositions and method steps, even if not specifically enumerated, are intended to be within the scope of the appended claims. Thus, combinations of steps, elements, components, or compositions are explicitly or hereafter referred to herein, but other combinations of steps, elements, components, and compositions are included, even if not explicitly stated.

[0177] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” include multiple references unless the context clearly indicates otherwise. Ranges may be expressed herein as “about” one particular value to and / or “about” another particular value. Where such ranges are expressed, other embodiments include one particular value to and / or another particular value. Similarly, where values ​​are expressed as approximations using the aforementioned “about,” it is understood that a particular value forms other embodiments. Furthermore, it is understood that each endpoint of a range is important both with respect to the other endpoints and independently of the other endpoints.

[0178] "Optional" or "optional" means that the event or situation described below may or may not occur, and that the description includes both cases in which such event or situation occurs and cases in which it does not.

[0179] Throughout this specification and claims, the words “equipped with,” and variations thereof such as “equipped with,” mean “including but not limited to,” and are not intended to exclude, for example, other additives, components, integers, or processes. The terms “essentially consisting of,” and “consisting of,” may be used in place of “equipped with,” and “containing,” to be provided for more specific embodiments of the invention, and are also disclosed. “Exemplary,” means “an example,” and is not intended to convey that a preferred or ideal embodiment is indicated. “Essentially,” is not used in an restrictive sense, but is used for descriptive or illustrative purposes.

[0180] Except as otherwise stated, all figures used in the specification and claims to represent shapes, dimensions, etc., should be understood not as an attempt to limit the application of the equivalence principle to the scope of the claims, and should be interpreted in terms of the number of significant figures and the usual rounding approach.

[0181] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in the field to which the disclosed invention pertains. Publications cited herein and the materials from which they are cited are incorporated specifically by reference.

Claims

1. A battery separator for enhancing acid mixing in a submersible lead-acid battery, It comprises a porous back web consisting of a first set of segmented ribs, a second set of segmented ribs, and a third set of segmented ribs, The first plurality of segmented ribs are arranged in the central portion of the porous back web, and the first plurality of segmented ribs include a plurality of row sections, each of which has a first row section and a second row section, the first row section and the second row section are arranged in a repeating manner, the first row section includes ribs arranged at an angle selected from the group consisting of greater than 45 degrees and less than 90 degrees and greater than 90 degrees and less than 135 degrees with respect to the width direction of the battery separator, and the second row section includes ribs arranged in a direction intersecting the ribs arranged in the first row section. The second set of segmented ribs are arranged in rows parallel to the left edge of the porous back web on the left side of the porous back web, alternating between areas with ribs and areas without ribs, with the areas without ribs staggered between adjacent rows, and The third set of segmented ribs are arranged in rows parallel to the left edge of the porous back web on the right side of the porous back web, alternating between areas with ribs and areas without ribs, with the areas without ribs arranged alternately between adjacent rows. The first plurality of segmented ribs are adjacent to the second plurality of segmented ribs, and the third plurality of segmented ribs are adjacent to the first plurality of segmented ribs. The battery separator is selected from the group consisting of ultra-high molecular weight polyethylene, rubber, polyvinyl chloride, phenolic resin, cellulose derivative, or a combination thereof.

2. The battery separator according to claim 1, wherein the ribs in the second row section intersect the ribs arranged in the first row section at a 90-degree angle.

3. The battery separator according to claim 1, further comprising one selected from the group consisting of a filler, a surfactant, or a combination thereof.

4. moreover, The battery separator according to claim 1, comprising an absorbent glass mat.

5. The battery separator according to claim 1, wherein the battery separator promotes or improves acid mixing more than a conventional solid rib contour separator having a plurality of solid ribs arranged at intervals in the vertical direction.

6. A submersible lead-acid battery comprising the battery separator described in claim 5.

7. A start / stop vehicle comprising the battery described in claim 6.

8. The vehicle according to claim 7, wherein the battery has a plate, the plate being arranged substantially parallel to the operating direction of the start / stop vehicle.

9. The battery separator is a negative electrode plate envelope, a battery separator for enhancing acid mixing in a submersible lead-acid battery according to claim 1.

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