JP2018530127A - Submerged lead-acid battery with improved performance, improved battery separator, and related methods - Google Patents

Abstract

An improved battery separator is disclosed herein for use in submerged lead acid batteries, and in particular, reinforced submerged lead acid batteries. The improved separator disclosed herein provides enhanced electrolyte mixing and a substantial reduction in stratification. The improved submerged lead acid battery may be advantageously used in applications where the battery remains partially charged, for example in a start / stop vehicle system. Also, improved lead-acid batteries, such as submerged lead-acid batteries, improved systems including lead-acid batteries and battery separators, improved battery separators, improved vehicles including such systems, and / or manufacturing and / or Or a method of use may be provided.

Description

(Cross-reference of related applications)
This application claims priority and benefit of co-pending US Provisional Patent Application No. 62/238373, filed Oct. 7, 2015, which is incorporated herein by reference in its entirety.

  In accordance with at least selected embodiments, the present disclosure or invention provides an improved lead acid battery, such as a submerged lead acid battery, an improved system including a lead acid battery and a battery separator, an improved battery separator, and such a system. Improved vehicles including and / or methods of manufacture and / or use. In accordance with at least certain embodiments, the present disclosure or invention provides an improved submerged lead-acid battery and / or an improved battery separator for such a battery, and / or the manufacture of such an improved submerged lead-acid battery. , Inspection and / or usage. In addition, disclosed herein are methods, systems, batteries, and battery separators for reducing stratification and extending battery life and performance in submerged lead-acid batteries.

  In order to reduce fuel consumption and the production of exhaust emissions, automakers have implemented varying degrees of electrical hybridization. One form of hybrid electric vehicle (HEV) is sometimes referred to as a “micro HEV” or “micro hybrid”. In such a micro HEV or similar vehicle, the automobile may have an idle start / stop (ISS) function, in which the engine may be at various points during idle start / stop and / or regenerative braking. You may stop at. This improves vehicle fuel efficiency, but also increases the burden on the battery that must provide power to auxiliary devices (such as air conditioners, media players, etc.) while the vehicle is stopped.

  Conventional vehicles (such as automobiles that do not have start / stop performance) may use conventional flooded lead acid batteries such as SLI lead acid batteries. Since the engine never stops, power is drawn from the battery only when the engine is cranked. At such times, the battery is typically in an overcharged state rather than a partially charged state. For example, such a conventional submerged lead acid battery appears to be more than 95% charged, more than 96%, more than 97%, more than 98%, more than 99%, or often overcharged. It can also be in a state of charge, charged even more than 100%. In overcharging, gas bubbles (for example, hydrogen gas bubbles) are generated in a conventional lead acid battery, and these circulating gas bubbles serve to mix a liquid electrolyte (acid) in the battery.

  On the other hand, the start / stop vehicle continuously draws power from the battery and is therefore always in a partially charged state. In partial charging, gas bubbles are not generated and mixing in the electrolyte is greatly reduced, leading to stratification in the battery. Thus, stratification is a problem in start / stop submersible lead-acid batteries and various reinforced submersible batteries, but is more traditional in operating with overcharge or full (or near full) charge. With traditional flooded lead acid batteries, there was no problem at all.

Stratification is a term for a process in which concentrated sulfuric acid is concentrated at the bottom of the cell and a correspondingly high water concentration is derived at the top of the cell. Stratification is not preferred in a submerged lead acid battery such as a reinforced submerged lead acid battery or a start / stop submerged lead acid battery. As the acid level at the top of the electrode decreases, uniformity and charge acceptance within the battery system may be hindered, and the variation in internal resistance from top to bottom along the height of the battery may increase. Increasing the acid level at the bottom of the battery can artificially increase the battery voltage, which can interfere with the battery management system, and send an unintended / false health signal to the battery management system. In general, stratification causes high resistance along the cell site, which may lead to electrode problems and battery life reduction. Start / stop the battery and / or other reinforcing flooded lead-acid battery, more and more popular with hybrid and fully electric vehicles, increasing vehicle fuel efficiency, if it is expected to reduce CO ₂ emissions There is a great need for a solution to reduce stratification and / or improve acid mixing.

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

  Therefore, there is a need for further development of reinforced submerged lead-acid batteries such as reinforced submerged start / stop batteries that do not undergo stratification during use. There is a need for an improved reinforced submerged lead acid battery that has improved uniformity and performance compared to those used so far and has performance comparable to that found in certain VRLA / AGM batteries. Yes.

  In accordance with at least selected embodiments, the present disclosure or invention may address the above and other needs. For example, according to at least certain embodiments, the present disclosure or invention provides a novel, improved or optimized submerged lead acid battery, system, and reinforced submerged lead acid battery separator, and their manufacture, inspection, and / or Target usage.

  Disclosed herein is a new, improved or optimized reinforced submerged lead acid battery having a particular type of separator. Surprisingly, by properly selecting the surface characteristics of the separator, stratification can be reduced and / or prevented and a corresponding increase in battery performance can be confirmed, which is related to a specific VRLA. It has been found that the performance of AGM batteries is close, consistent or even better. Furthermore, surprisingly, by using the separators described herein in conjunction with the batteries described herein, and using them in motion, this of the inventive batteries and separators can be achieved. Such movement facilitates improving acid mixing or circulation and / or reducing or preventing stratification without requiring any mechanical means or any acid mixing tool (such as an acid mixing pump). It has been found. Various embodiments are described in further detail below.

  In accordance with at least selected embodiments, aspects or purposes, the present disclosure or invention provides an improved lead acid battery, such as a submerged lead acid battery, an improved system including a lead acid battery and a battery separator, an improved battery separator, and the like. Intended for improved vehicles and / or methods of manufacture and / or use including such systems.

  In accordance with at least selected embodiments, aspects or objectives, the present disclosure or invention has been used in the past, reinforced submersible lead-acid batteries, such as reinforced submersible start / stop batteries, that do not undergo stratification during use. To provide an improved reinforced submerged lead acid battery having improved uniformity and performance compared to that and / or an improved reinforced submerged lead acid battery having performance at least comparable to or exceeding certain VRLA AGM batteries. May be.

FIG. 1 shows a cell (top row) having separators with serrated ribs according to the present invention (these serrations may also be referred to as an embedding rib or an embedding), vertically along the separator. A series of photographs are included comparing to a cell with a conventional solid ribbed separator (bottom row). The interval between the ribs for the separator shown in the upper row (from the tip of the rib to the tip of the rib) was about 11 mm. FIG. 1 shows the surface of a battery separator that typically faces the positive electrode of a submerged lead-acid battery (such as a submerged submerged lead-acid battery). However, such ribs may be included on both sides of the separator (for example, it may be included on the surface of the separator designed to face the negative electrode of the submerged lead-acid battery). The cell shown in FIG. 1 has undergone 90 start / stop events or cycles. As shown in FIG. 1, after 30, 60, and 90 start / stop events or cycles, the stratification shown by the cell with the serrated ribbed separator is significantly greater than the cell with the conventional separator. Few. FIG. 2 compares the same type of cells (upper row) with a separator with serrated ribs according to the present invention (upper row) with cells having a conventional separator with conventional solid ribs (lower row). A series of photos are included. The cell received 60 start / stop events or cycles in a vehicle traveling at 25 mph after overnight rest. As shown in FIG. 2, the stratification exhibited by the cell with the separator with the ribbed ribs is significantly less than the cell with the conventional separator. Such an examination demonstrated the experimental results shown in the photograph of FIG. In FIG. 3, cells having closer spaced serrated rib separators according to the present invention (upper row) are shown as cells having conventional solid ribbed separators that are perpendicular along the separator (lower row). A series of photos being compared to are included. The spacing of the envelope ribs relative to the separator shown in the upper row was about 7 mm. The cell received 90 start / stop events or cycles. As shown in FIG. 3, after 30, 60, and 90 start / stop events or cycles, the stratification shown by the cell with the serrated ribbed separator is significantly greater than the cell with the conventional separator. Few. In FIG. 4, cells having separators with dimples according to the present invention (upper row) are replaced with cells having conventional separators including solid large and solid small ribs extending vertically along the separator (lower row). ) Is included. The cell received 90 start / stop events or cycles. As shown in FIG. 4, after 30, 60, and 90 start / stop events or cycles, the stratification shown by the cell with the dimpled separator is significantly less than the cell with the conventional separator. Thus, solid ribs (eg, as shown in the bottom row of FIG. 4) actually inhibit acid mixing for the separator in the start / stop lead acid battery. FIG. 5 shows cells (upper rows) having separators with dimples according to the present invention (lower rows) with cells having separators including solid ribs extending vertically along the separators coupled to the dimples. Includes a series of photos being compared. The cell received 90 start / stop events or cycles. As shown in FIG. 5, the stratification shown by the cells with the dimpled separator (upper row) is the lower row start / stop lead acid battery cell with the separator containing the combination of dimple and solid rib. Less than. However, some acid mixing is shown in the bottom row (eg, compared to the bottom row of the photos of FIGS. 1-4). For example, in some of the pictures in the bottom row, a clear region or pocket with low acid concentration is seen, but acid mixing is also seen. The photographs in the bottom row show that a combination of serrations and solid ribs or dimples and solid ribs may prove useful in various batteries, systems and methods according to the present invention. FIG. 6 shows a separator with solid ribs extending diagonally along the separator (at a slight angle with respect to the vertical direction of the separator) with cells (upper row) having dimpled separators according to the invention. A series of photographs comparing to cells having The cell received 90 start / stop events or cycles. As shown in FIG. 6, the stratification shown by cells with dimple separators (upper row) is a photographic start / stop lead acid battery cell like that shown in the lower row of FIGS. Fewer. Regarding the bottom row of the picture in FIG. 6, it can be seen that at 60 cycles or 60 start / stop events, some stratification is still present, but stratification improves at 90 cycles. . 7 (A) and 7 (B) include comparative photographs of a conventional solid rib separator (A) and no separator (B) in a jar filled with mixed 1.28 specific gravity acid. It is. FIG. 7A includes a photograph of a conventional ribbed separator, showing stratification with red acid concentration at the bottom of the jar and a clear liquid toward the top of the jar. FIG. 7B includes a photograph of only a lead grid electrode without a separator, and the occurrence of stratification is much less, as shown in red over the jar. 7 (A) and 7 (B) serve to illustrate that a conventional separator with solid ribs may prevent acid mixing inside the start / stop submersible lead-acid battery and promote stratification. Similarly, FIG. 7B provides a kind of benchmark that does not include a separator against which various separators can be compared. FIG. 8 includes a photograph of a cell constructed using the separator with ribs according to the present invention prior to inspection for stratification. FIG. 9 includes a photograph of the cell of FIG. 8 summarized in a case for stratification inspection. Lead straps are installed across the electrode + separator group. Once acid is added to the case, the acid level may be a few millimeters above these lead straps (just as an example, in some cases, about 3 mm above the lead strap). When this case, including electrodes and separators, is inspected for stratification in the cell, in certain embodiments, the direction of the inspection movement mimics the movement of the start / stop electric vehicle, the vehicle is moved and accelerated. 9 is preferably in the y direction of the photograph of FIG. 9 so that the acid is moved across the surface of the electrode so that it is decelerated and stopped. This figure shows that the top of the photo in FIG. 9 extends toward the front bumper of the electric vehicle having start / stop performance, while the bottom of the photo in FIG. 9 extends toward the rear bumper of the electric vehicle and is soon stratified. It may appear that the group of electrode + separator + lead strap filled with test acid is looked down. FIG. 10 includes photographs of cross-sectional views of serrations or serrated ribs on separators utilized in accordance with various embodiments described herein. FIG. 11 includes two views of the contours of a serrated separator utilized in accordance with various embodiments described herein. FIG. 12 shows a graph of the conductivity of the sulfuric acid solution at 25 ° C. The graph helps to understand that stratification can lead to non-uniform currents due to conductivity differences in the high and low acid regions of the cell and / or battery. FIG. 13 includes a picture of a cell configured similar to the cell shown in FIG. However, for the cell shown in FIG. 13, the separator was inserted into a system perpendicular to the direction of vehicle movement (while for the cell shown in FIG. 6, the separator was described in the direction of FIG. 9 above. As well as inserted in a system parallel to the direction of movement). In various embodiments, the separator is preferably positioned parallel to the direction of movement relative to the vehicle and battery system. This is because the photograph shown in FIG. 13 reveals that stratification still occurs after 60 start / stop events or cycles without good acid mixing. Using the top row of FIG. 13 as an example, where a dimpled separator is utilized in accordance with various embodiments of the present invention, all due to battery and separator placement in the system, It occurred and acid mixing was not optimal. FIG. 14 includes photographs of battery separators including serrated ribs according to various embodiments described herein. This separator was used to wrap an electrode for making a submersible lead-acid battery for start / stop automobiles for inspection. The result of the inspection will be described later. 15A (A) and 15 (B) include illustrations of a plurality of serration profiles for a separator according to various embodiments herein. Various optimal profiles for separators to improve and enhance acid mixing are disclosed herein. The illustrations shown in FIGS. 15A (A) and (B) are merely examples of such optimal contours, and an improved separator in which many other optimal contours are described and claimed herein. , Batteries, systems, and methods. 15B (C) and 15 (D) include illustrations of a plurality of serration profiles for separators according to various embodiments herein. Various optimal profiles for separators to improve and enhance acid mixing are disclosed herein. The views shown in FIGS. 15B (C) and 15 (D) are merely examples of such optimal contours, and an improved separator in which many other optimal contours are described and claimed herein. , Batteries, systems, and methods. FIG. 16 includes a graph showing a cycle test for an example of a reinforced submerged battery (or a submerged battery operating in reinforced mode). In today's newer battery applications, reinforced submersibles operate at a lower charge than previously known submerged lead-acid batteries (often operated with overcharge or greater than 100% charge). doing. Thus, such reinforced submerged cells are less than 95%, in some cases less than 90%, in some cases less than 85%, in some cases less than 80%, in some cases less than 70% and in some cases less than 60%. In some cases, it may be operating in a state of charge (SoC) of less than 50%, in some cases less than 25%, and in some cases even less than 10%. In this particular graph, the cycle test was performed on a 17.5% depth of discharge (DoD) battery and the separator utilized was a conventional one such as that shown in the lower row of the photograph of FIG. It was a ribbed separator. This particular battery delivered energy under high cycling conditions in a partially discharged state of charge and showed the ability to work well in a lead sulfate rich environment. Batteries such as those tested with respect to FIG. 16 and utilized in start / stop applications dramatically increased energy throughput compared to standard SLI batteries (such as those shown in standards such as EN50342). . Because such reinforced submersible batteries and / or submerged batteries for start / stop applications operate in a partially charged state, they need to have higher charging efficiency and / or be charged more quickly. In some cases, reinforced submerged batteries use various additives with one or more electrodes to create a battery that increases charging efficiency and / or receives more quickly. However, the reinforced separators described herein can achieve the same goal.

  In various embodiments described herein, separators that enhance electrolyte mixing and / or circulation in submerged lead-acid batteries are used. In certain embodiments, separators that reduce stratification are used. In various embodiments, a battery is disclosed in which stratification is significantly reduced compared to known batteries because of improved or enhanced separator systems for acid mixing and anti-stratification. Such a battery may be used, for example, in a moving vehicle having a battery. Also, in various embodiments, the movement of a vehicle (eg, an electric vehicle including a start / stop lead acid battery) to actually mix the acid or electrolyte is coupled with the reinforced battery separator described herein. In this specification, as well as the significant improvement in acid mixing shown herein, in start / stop submersible lead-acid batteries and / or reinforced submersible lead-acid batteries or batteries operating in enhanced mode. Unexpectedly reduces the stratification shown in For example, stop / start of a start / stop electric vehicle is supplying energy in various embodiments herein, mixing acid / electrolyte in a reinforced submerged lead acid battery, improving acid mixing, Reduce or completely prevent stratification.

  In accordance with at least certain embodiments, the polyolefin separator can be a sheet of polyolefin having serrated ribs, protrusions, embossments, dimples, embossments, and combinations thereof on one or more of its surfaces. In other embodiments, the polyolefin separator can be a sheet of polyolefin combined with certain additives and having serrated ribs, protrusions, emplacements, dimples, embossments on one or more of its surfaces.

  The separator is preferably made of polyolefin, for example polypropylene, ethylene-butene copolymer, preferably polyethylene, more preferably high molecular weight polyethylene, i.e. polyethylene having a molecular weight of at least 600,000, or high density polyethylene, for example at least Polyethylene having a molecular weight of 500,000. In some embodiments, one or more ultra high molecular weight polyethylene is utilized. That is, a polyethylene having a molecular weight of at least 1,000,000, in particular more than 4,000,000, and in some cases (measured by viscosity measurement and calculated by the Margolies equation) 5,000,000 to 8,000 , 000, substantially zero standard load melt index (as specified and measured in ASTM D1238 (Condition E) using a standard load of 2,160 g) and a viscosity number above 600 ml / g, 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 polyolefin in 100 g decalin at 130 ° C.).

  According to at least one embodiment, the separator comprises ultra high molecular weight polyethylene (UHMWPE) mixed with process oil and silica, eg, precipitated silica and / or fumed silica. In accordance with at least another embodiment, the separator consists of ultra high molecular weight polyethylene (UHMWPE) mixed with process oil, additives and silica, eg, precipitated silica. The separator preferably comprises a homogeneous mixture of 8 to 100% by volume of polyolefin, 0 to 40% by volume of plasticizer and 0 to 92% by volume of inert filler. In some cases, a suitable filler is dry, finely divided silica. However, the fillers are silica, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolite, 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, and the like, and various combinations thereof.

  Suitable plasticizers are petroleum and / or waxes. Since the plasticizer is the most easily removed component from the polymer-filler-plasticizer mixture, it helps to impart porosity to the battery separator.

  The separator has an average pore size of less than 1 μm in diameter. 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.

  In some cases, the pore size may be liter, H.P. L. , And Drake, L. C. In addition, the mercury intrusion method described in Industrial and Technical Chemical Analysis 17th edition, 787 (1945) may be used. According to this method, mercury is introduced into pores of different sizes by changing the pressure applied to the mercury using a porosimeter (Porosimeter Model 2000, Carlo Elba). The pore distribution may be determined by evaluation of unanalyzed data with MILESTONE 200 software.

  The thickness of the separator is preferably larger than 0.1 mm and not larger than 5.0 mm. The thickness of the separator is 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 thickness takes into account the thickness of the entire separator including any selected 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 attached to its surface.

  In various embodiments, the microporous polyolefin separator layer includes ribs such as serrated ribs. Suitable ribs may be placed between 0.001 mm and 20 mm apart at a height of 0.008 mm to 1 mm. On the other hand, a suitable backweb thickness of a microporous polyolefin separator layer without serrated ribs or embossing may be from about 0.05 mm to about 0.500 mm (eg, in certain embodiments, about 0.25 mm). Good. For example, the rib 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, 0.9 mm, 1.0 mm, .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. In some embodiments, the ribs may be in a pattern such that the mutual relationship is 0-90 degrees and is on one side of the separator layer or on both sides of the polyolefin separator. Various patterns including ribs on both sides of the separator layer may include negative lateral ribs on the second side or back of the separator. Such negative lateral ribs may optionally have a height of 0.025 mm to about 0.1 mm.

  The ribs may have serrations in certain preferred embodiments. The serration may have an average tip length of 0.05 mm to 1 mm. For example, the average chip length is 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 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.

  The serration may have an average baseline length of 0.05 mm to 1 mm. For example, the average baseline length is 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 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.

  The serration may have an average height of 0.05 mm to 4 mm. For example, the average height is 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 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. For embodiments where the height of the serration is the same as the height of the rib, the serrated rib may be referred to as a protrusion. Such a range may apply to industrial start / stop main battery separators, and the overall thickness of the separator may typically be from about 1 to about 4 mm. Similarly, an automotive start / stop battery may have a slightly thinner overall separator thickness (eg, typically about 0.3 mm to about 1 mm).

  The serration may have an average center to center pitch of 0.1 mm to 50 mm. For example, the average center-to-center pitch is 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 0.5 mm or more and / or 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. It can be 2 mm or less.

  The serration may have an average height base width ratio of 0.1: 1 to 500: 1. For example, the average height base width ratio is 0.1: 1, 25: 1, 50: 1, 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1, or 450. : 1 or more and / or 500: 1, 450: 1, 400: 1, 350: 1, 300: 1, 250: 1, 200: 1, 150: 1, 100: 1, 50: 1, or 25: It can be 1 or less.

  The serration may have an average bottom width tip width ratio of 1000: 1 to 0.1: 1. For example, the average bottom width chip width ratio is 0.1: 1, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 15: 1, 20: 1, 25: 1, 50: 1, 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1, 450: 1, 500: 1, 550: 1, 600: 1, 650: 1, 700: 1, 750: 1, 800: 1, 850: 1, 900: 1, 950: 1 or more, and / or 1000: 1, 950: 1, 900: 1, 850: 1, 800: 1, 750: 1, 700: 1, 650: 1, 600: 1, 550: 1, 500: 1, 450: 1, 400: 1, 350: 1, 300: 1, 250: 1, 200: 1, 150: 1, 100: 1, 50: 1, 25: 1, 20: 1, 15: 1, 10: 1, 9 1,8: 1,7: 1,6: 1,5: 1,4: 1,3: 1,2: 1, or 1: it may be 1 or less.

  In some embodiments, the separator can be dimples. Dimples are typically protruding features on one or more surfaces of the separator. The thickness of the dimple can be 1 to 99% of the thickness of the separator. For example, the average thickness of the dimples is 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40% of the average thickness of the separator. , 35%, 30%, 25%, 20%, 15%, 10%, or 5%. The dimples may be arranged in the row direction along the separator. Rows or lines may be placed 0.001 mm to 10 mm apart. For example, the rows are 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, .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. On the other hand, the dimples may be arranged in a random arrangement or randomly.

  The dimples may have an average dimple length of 0.05 mm to 1 mm. For example, the average dimple length is 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 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.

  The dimples may have an average dimple width of 0.01 mm to 1 mm. For example, the average dimple width is 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 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.

  The dimples can have an average center-to-center pitch of 0.1 mm to 50 mm. For example, the average center-to-center pitch is 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 0.5 mm or more and / or 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. It can be 2 mm or less.

  The dimple can be, for example, a square and a rectangular quadrangle. The dimples may have an average dimple length dimple width ratio of 0.1: 1 to 100: 1. For example, the average long bottom width ratio is 0.1: 1, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1. 10: 1, 15: 1, 20: 1, 25: 1, 50: 1, 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1, 450: 1, 500 1: 550: 1, 600: 1, 650: 1, 700: 1, 750: 1, 800: 1, 850: 1, 900: 1, 950: 1 or more, and / or 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, : 1,7: 1,6: 1,5: 1,4: 1,3: 1,2: 1, or 1: it may be 1 or less.

  In some embodiments, the dimples can be substantially circular. The circular dimple may have a diameter of about 0.05 to 1.0 mm. For example, the average dimple diameter is 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 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.

  Various other shapes of dimples may be included as well. By way of example only, such dimples may be triangular, pentagonal, hexagonal, heptagonal, octagonal, etc.

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

  Table 1 directly below shows the serrations and / or dimples used in forming separators to prevent stratification and to increase acid mixing in submerged lead-acid batteries (sometimes referred to as reinforced submerged batteries). Includes multiple specific embodiments of separators having various parameters.

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

  The separator utilized in the various embodiments herein may comprise one or more additives. In such cases, the additive may strengthen the separator for a specific stop / start submerged lead acid battery for a specific 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 alkyl sulfates, alkyl aryl sulfonate salts, alkyl phenol-alkylene oxide addition products, soaps, alkyl naphthalene sulfonates, dialkyl esters of sulfosuccinates, quaternary amines, ethylene oxide and propylene oxide blocks. Copolymers and surfactants such as salts of mono and dialkyl phosphate esters. Additives include 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, organosilicone surfactants, ethylene vinyl It can be a nonionic surfactant such as acetate terpolymer, ethoxylated alkylaryl phosphate ester and sucrose fatty acid ester.

In certain embodiments, the additive can be represented by a compound of formula (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 oxygen atoms.
R ¹ is H, — (CH ₂ ) _k COOM ^{x +} _{1 / x} or — (CH ₂ ) _k —SO ₃ M ^{X +} _{1 / X} , preferably H, where k is 1 or 2.
M is an alkali metal or alkaline earth metal ion, H ⁺ or NH ₄ ⁺ , where not all variables M have the meaning of H ^{+ at} the same time.
n is 0 or 1.
m is 0 or an integer of 10 to 1400.
x is 1 or 2.
The oxygen atom carbon atom ratio in the compound according to formula (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 zero.

  By non-aromatic hydrocarbon group is intended a group that does not contain an aromatic group or represents itself. Hydrocarbon groups can be interrupted by oxygen atoms, ie contain one or more ether groups.

  R is preferably a linear or branched aliphatic hydrocarbon group that can be blocked by an oxygen atom. Saturated, uncrosslinked hydrocarbon groups are very suitable.

By using the compounds of formula (I) in the manufacture of various battery separator additives as described herein, such separators may be provided with effective protection against oxidative breakdown. In some embodiments, a battery separator including an additive containing a compound according to formula (I) is suitable. here,
R is carbonized with 10 to 180, preferably 12 to 75 and very preferably 14 to 40 carbon atoms which can be interrupted by 1 to 60, preferably 1 to 20 and very preferably 1 to 8 oxygen atoms. A hydrogen group, particularly preferably a hydrocarbon group of the formula R ² — [(OC ₂ H ₄ ) _p (OC ₃ H ₆ ) _q ] —. here,
R ² is an alkyl group having 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 carbon atoms.
P is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4.
q is an integer of 0 to 30, preferably 0 to 10, particularly preferably 0 to 4.
The compound is particularly preferably such that the sum of p and q is 0-10, especially 0-4.
n is 1.
m is 0.
The formula R ² -[(OC ₂ H ₄ ) _p (OC ₃ H ₆ ) _q ] — also includes those compounds, but those that differ from those in which the sequence of groups in square brackets is shown. Is understood as being. For example, according to the present invention, compounds are also suitable in which the group in parentheses replaces the (OC ₂ H ₄ ) group and the (OC ₃ H ₆ ) group.

Additives in which R ² is a linear or branched alkyl group having 10 to 20, preferably 14 to 18 carbon atoms have proven particularly advantageous. OC ₂ H ₄ preferably represents OCH ₂ CH ₂ and OC ₃ H ₆ represents OCH (CH ₃ ) CH ₂ and / or OCH ₂ CH (CH ₃ ).

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

  Additives of type m = 0 that are insoluble or only partially soluble in water and sulfuric acid have proven particularly advantageous.

Also suitable are additives comprising compounds according to formula (I). here,
R is an alkane group having 20 to 4200, preferably 50 to 750 and very preferably 80 to 225 carbon atoms.
M is an alkali metal or alkaline earth metal ion, ^{H +} or _NH ^{4 +,} in ^particular, Li +, a Na ⁺ and ^{K +} or ^{H +} and the like of alkali metal ions, all variables M simultaneously ^{H +} meanings Does not have.
n is 0.
m is an integer of 10 to 1400.
x is 1 or 2.

As suitable additives, mention may in particular be made of polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers, whose acid groups are at least partly, ie preferably 40%, in particular Preferably, it is neutralized by 80%. The ratio refers to the number of acid groups. Polyacrylic acid (polymethacrylic acid) which is entirely present in the salt form is very suitable. By polyacrylic acid (polymethacrylic acid), polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymers are contemplated. Polyacrylic acid (polymethacrylic acid), in particular 1,000 to 100,000 g / mol, particularly preferably 1,000 to 15,000 g / mol and very particularly preferably 1,000 to 4,000 g / mol of average molar mass Polyacrylic acid having _Mw is preferred. The molecular weight of the polyacrylic acid (polymethacrylic acid) polymer and copolymer is confirmed by measuring the viscosity of a 1% aqueous solution neutralized with a sodium hydroxide solution of the polymer (Fikencher's constant).

  A copolymer of acrylic acid (methacrylic acid), in particular a copolymer containing ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and / or ethylhexyl acrylate as a comonomer in addition to acrylic acid (methacrylic acid). Polymers are also suitable. Copolymers containing at least 40% by weight, preferably at least 80% by weight of acrylic acid (methacrylic acid) monomer are suitable, the proportions being based on the acidic form of the monomer or polymer.

  For neutralizing polyacrylic acid polymers and copolymers, alkali metal and alkaline earth metal hydroxides such as potassium hydroxide and especially sodium hydroxide are particularly suitable.

  The microporous polyolefin may contain an additive or multiple additives in a variety of ways. The additive can be applied to the polyolefin, for example, when finished (ie, after extraction) or added to a mixture utilized to produce the polyolefin. According to a preferred embodiment, the additive or additive solution is applied to the surface of the polyolefin. This variant is particularly suitable for the application of non-heat stable additives and additives that are soluble in the solvents used for subsequent extraction. Particularly suitable as solvents for the additives according to the present invention are mixtures of these alcohols and water, as well as low molecular weight alcohols such as methanol and ethanol. The application can be applied to the side of the separator facing the negative electrode, the side facing the positive electrode, or both sides.

The additive is at least 0.5 g / m ² , 1.0 g / m ² , 1.5 g / m ² , 2.0 g / m ² , 2.5 g / m ² , 3.0 g / m ² , 3.5 g / M ² , 4.0 g / m ² , 4.5 g / m ² , 5.0 g / m ² , 5.5 g / m ² , 6.0 g / m ² , 6.5 g / m ² , 7.0 g / ^{m 2, 7.5g / m 2,} 8.0g / m 2, 8.5g / m 2, 9.0g / m 2, can be present in a concentration of 9.5 g / ^{m 2} or 10.0 g / ^{m 2} . ^{Additives, 0.5~10g / m 2, 1.0~10.0g /} m 2, 1.5~10.0g / m 2, 2.0~10.0g / m 2, 2.5~ ^{10.0g / m 2, 3.0~10.0g / m} 2, 3.5~10.0g / m 2, 4.0~10.0g / m 2, 4.5~10.0g / m 2 5.0-10.0 g / m ² , 5.5-10.0 g / m ² , 6.0-10.0 g / m ² , 6.5-10.0 g / m ² , 7.0-10 0.0 g / m ² , 7.5 to 10.0 g / m ² , 5.0 to 10.5 g / m ² , 5.0 to 11.0 g / m ² , 5.0 to 12.0 g / m ² , Or it may be present in the separator at a concentration between 5.0 and 15.0 g / m ² .

  Application may also be performed by immersing the polyolefin in an additive or a solution of the additive followed by optional removal of the solvent, for example by drying. In this way, the application of additives can be combined with extraction, which is often carried out, for example, during polyolefin production.

  The separators, methods, batteries, and battery systems described herein may take a long time to reduce stratification and improve electrolyte circulation and mixing. This is particularly important for deep circulation and / or reinforced submersible lead acid batteries where stratification can significantly reduce battery performance. Various submerged lead acid batteries, reinforced submerged lead acid batteries, and applications thereof 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, folk trucks, golf carts, neighborhood electric vehicles, etc., especially not fully charged or 100% charged (or overcharged) ) 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.

  The reinforced submerged battery, particularly the reinforced submerged separator described herein (also referred to as an acid-mixed separator) for use in a mobile battery, surprisingly and unexpectedly, is such a reinforcement. Submersion cells are provided with a significant improvement in acid mixing and / or acid circulation, resulting in a significant reduction or complete prevention of stratification in reinforced submersion cells. This may be extremely important because the acid flow and circulation along the entire separator means that the entire battery is utilized for several smaller parts of the battery in use. . That is, using the enhanced separator, battery, system, and method of the present invention, the electrolyte (eg, sulfuric acid) is free to flow to and along all or nearly all parts of the separator. Thus, it flows freely to and along all or nearly all of the positive and negative electrode active materials of the electrode. On the other hand, stratification (see, for example, stratification in the bottom row of the photos of FIGS. 1-4, where a red indicator is added to the acid. Clear liquid, ie water clearly Visible and present in the upper half of the test cell, whereas acid is clearly visible and present in the lower half of the test cell.) The entire cathode active material and anode active material on either side is completely devoid of acid, so use the full potential to power the underlying device / vehicle using batteries. I can't. Thus, the improved separators, batteries, systems, and methods described herein greatly reduce stratification in submerged lead acid batteries, such as reinforced submerged batteries.

The reason for concern for stratification is that it results in current density non-uniformity across the surface of the positive and negative plates or positive and negative electrodes. The graph shown in FIG. 12 shows the conductivity of H ₂ SO ₄ versus concentration.

  In some preferred embodiments of the present invention, serrations present on one or more surfaces of the separator are non-uniformly distributed. Further, in some preferred embodiments, dimples present on one or more surfaces of the separator are non-uniformly distributed. For example, the serrations and dimples themselves may be non-uniform in size (eg, may be randomly formed), and the serration and / or dimple spacing may be random and / or non-uniform. By way of example, the various serrations and / or dimples utilized herein may be present on one or both sides of the separator in a regular or irregular arrangement. Further, the various ribs utilized herein, such as the serrated ribs, may be non-linear. For example, depending on the selected rib, a wavy pattern or a non-linear pattern may be used.

  In various embodiments, the effect of the reinforced submersible separator for the reinforced submerged battery described herein stands out because the reinforcement to the separator is parallel to the direction of movement of the moving battery. This is the case when the separator is placed in a reinforced submerged battery so as to extend. Such an effect can be understood by comparing the desired result of FIG. 6 with the less desirable result of FIG. In the photograph of FIG. 13, stratification is still observed despite the use of a separator with an enhanced profile for acid mixing. This is because the cell of FIG. 13 is positioned such that the reinforcement in the separator and electrodes is perpendicular to the direction of movement of the battery in the vehicle. The arrangement of the battery in the car with electrodes and separators parallel to the start and stop inertia allows better acid mixing than vertical positioning. When vertical, the electrodes and separator prevent rather than promote acid turbulence and acid mixing.

  The various reinforced separators described herein, for example, reinforced separators having serrations to improve acid mixing and acid cycling, may have various spacings and / or various patterns. By way of example only, FIGS. 15A-15D show examples of serrated ribs that may be effective in the present invention. Such patterns, and other patterns (both uniform and non-uniform, and both regular and irregular), as well as other major improvements in battery electrical characteristics, The ranking amperage (CCA) may be improved. In a serrated pattern, such as that in FIGS. 15A-15D (by way of example only), a solid rib (control means) that makes it possible to reduce the ribs in contact with the positive electrode active material (PAM) resulting in improved CCA performance ), The surface area is reduced by about 53%. In such a pattern, such as that shown in FIGS. 15A-15D, the rib mass may be reduced by 33% compared to a solid rib profile (control means) that can increase acid utilization and improve performance. Furthermore, it may be important to maintain positive electrode active material (PAM) compression with a balance of rib mass and opening for acid mixing and acid utilization.

  Furthermore, the arrangement and design of the protrusions (such as dimples, serrations, etc.) are preferably optimized for compression so as not to promote PAM discharge, preferably from an intimate relationship with the positive grid frame or current collector It is supported across the grid frame so as not to extrude the pellets.

  The battery of the present invention may be provided to reduce the cost by reducing the lead required for superior performance resulting from increased utilization of PAM. This may also allow for battery cost reductions required by automakers, and also battery weight reductions required by automakers.

  In some cases, the reinforced separator utilized in the present invention is 10-90% of the surface area of conventional ribs, preferably 30-70% of the surface area of conventional ribs, more preferably, in some cases, that of conventional ribs. It may have an optimized profile with the rib surface area compared to the rib surface area of a conventional rib profile, such as a solid vertical rib profile that is 40-60% of the surface area. All of this depends on the ultimate goal of improving rib shape, rib spacing, and acid mixing and preventing stratification, all of which are optimized.

[Example]
8 and 9 show battery experiments performed in a cell container. The battery test cell shown in these pictures along with a white case and a group of lead electrodes had the following general characteristics.

  In the additional example shown below, expanded battery test data for commercial group 3119 plates / group Ca / Ca is shown. In this table, the separator marked “new” has the serration profile shown in the envelope of FIG. On the other hand, the result marked “control” has solid ribs perpendicular to the separator. These results revealed unexpected and / or surprising results with respect to improved battery performance for start / stop reinforced submerged lead-acid batteries using reinforced separators according to the present invention. The results in the table below showed a significant improvement even when the battery was not installed in a large movement in the car, but rather in general movement while moving around in the inspection facility. In this way, combined with movement from the vehicle and / or energy from various start / stop events, the battery performance results may be further improved significantly.

  The importance of this Midtronics CCA test is not a global standard test, but a handheld device that uses algorithms to calculate battery performance quickly and easily. Increasing the surface area of the positive grid exposed to acid using an acid-mixed separator can improve conductivity and improve electrode performance. Although it is not an industry standard, it is used today in purchasing decisions around the world due to its ease of use. Improving the performance of this algorithm tester is key to customer satisfaction, and improvements in acid-mixed separators facilitate the results as shown in Table 3 #.

  The compositions and methods of the appended claims are not limited in scope to the specific compositions and methods described herein, but the specific compositions and methods described herein are claimed. This is intended to describe a few aspects. Any functionally equivalent compositions and methods are intended to be within the scope of the claims. In addition to what is shown and described herein, various compositional and method variations are intended to be within the scope of the appended claims. Further, only specific representative compositions and method steps disclosed herein have been specifically described, but other combinations of compositions and method steps have not been specifically listed. Are intended to be within the scope of the appended claims. As such, combinations of steps, elements, components, or configurations are explicitly referred to herein or below, but other combinations of steps, elements, components, and configurations are also expressly stated. Not mentioned but included.

  As used herein, the term “comprising” and variations thereof are used as synonyms for the term “including” and variations thereof, and are open, non-limiting It is a simple term. The terms “comprising” and “comprising” are used herein to describe various embodiments, but the terms “consisting essentially of” and “consisting of” The terminology can be used in place of “comprising” and “including” to provide for a more specific embodiment of the present invention and is also disclosed. Except as noted, all numbers representing shapes, dimensions, etc. utilized in the description and claims are not at least an attempt to limit the application of equivalent principles to the scope of the claims. Should be interpreted in terms of the number of significant digits and the usual rounding approach.

  Unless defined otherwise, all technical and scientific terms utilized herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference.

Claims (15)

An improved stop / start submersible lead acid battery,
Comprising a microporous polyolefin battery separator comprising serrated ribs, interrupted ribs, dimples or combinations thereof;
The stop / start submerged lead acid battery has an enhanced or improved acid mix and / or reduces stratification compared to conventional stop / start or ISS submerged lead acid batteries.   The battery of claim 1, wherein the microporous polyolefin battery separator comprises polyethylene.   The battery according to claim 1, wherein the battery separator further includes a filler.   The battery according to claim 1, wherein the battery separator further includes a surfactant or an additive. Comprising a separator having a plurality of rows of serrated ribs, intermittent ribs, dimples, or combinations thereof;
The battery according to claim 1, wherein the rows are placed 0.1 to 20 mm apart. The battery is running,
6. A battery according to any one of the preceding claims, wherein the movement provides energy for the strengthening or improved acid mixing. A method for reducing stratification in a battery, comprising:
Providing an alternating sequence of positive and negative electrodes;
Providing a separator between each of the electrodes, the separator comprising a microporous polyolefin battery separator, the separator having a serrated rib, an interrupted rib, a dimple or a combination thereof;
Immersing the electrode in a liquid electrolyte;
A method comprising:   A reinforced submerged battery, wherein the improvement includes the battery according to any one of claims 1 to 6.   A reinforced submerged battery comprising the separator according to any one of claims 1 to 6.   Solid rib separator, comprising a serration mechanically induced by creasing at the nip point or by calendering.   A method of inspecting a battery by inducing acceleration / deceleration movement to promote acid mixing in the presence of an acid mixing separator, thereby reducing stratification.   Separator with reduced mass resulting from reduced acid substitution, making the electrolyte between the electrodes more suitable for use.   A separator that improves the conductivity of the battery, allowing for improved health and / or communication with an electronic device in the battery monitoring system or battery management system as placed in a vehicle or handheld monitoring device Separator.   Improved lead-acid batteries such as submerged lead-acid batteries, improved systems including lead-acid batteries and battery separators, improved battery separators, improved vehicles including such systems, and / or manufacturing and / or use Method; improved submerged lead-acid battery and / or improved battery separator for such a battery, and / or method of manufacturing, testing and / or using such improved submerged lead-acid battery; Methods, systems, batteries, and battery separators for reducing stratification and extending battery life and performance in type lead acid batteries; and / or improvements such as enhanced flooded start / stop batteries that do not undergo stratification during use or Enhanced submerged lead acid batteries, improvements with improved uniformity and performance compared to previously available, enhanced submerged lead acid batteries, and / or Flooded lead-acid battery improved, enhanced with comparable or greater than the performance for at least certain VRLA · AGM batteries. An improved submerged lead-acid battery,
Equipped with a microporous polyolefin battery separator,
The separator has a serrated rib, an intermittent rib, a dimple or a combination thereof.
The stop / start submerged lead acid battery is a battery with enhanced or improved acid mixing and / or reduced stratification compared to conventional submerged, stop / start or ISS submerged lead acid batteries.