KR102173880B1 - Improved separators, batteries, systems, and methods for idle start stop vehicles - Google Patents

Abstract

According to one embodiment of the present invention, an improved, unique, and/or high-performance ISS lead-acid battery separator, e.g. an improved ISS open lead-acid battery separator, an ISS vehicle battery comprising such a separator, a manufacturing method and a method of use Is provided. Preferred ISS separators may include negative cross ribs and/or PIMS minerals. According to an embodiment of the present invention, PIMS minerals, preferably fish meals, biominerals replace some of the silica fillers in a silica-filled lead acid battery separator, preferably a polyethylene/silica separator formulation. According to embodiments of the present invention, new or improved batteries, separators, components, and/or compositions having heavy metal removal capabilities, and/or methods of making and/or using them are addressed.

Description

Improved separators, batteries, systems and methods for idle start stop vehicles {IMPROVED SEPARATORS, BATTERIES, SYSTEMS, AND METHODS FOR IDLE START STOP VEHICLES}

Cross-reference related to application

This application is filed on September 22, 2010 by Whear et al., US provisional application No. 61/385,285 and Whear et al. No. 61/532,598, filed September 9, 2011, claim priority, which are incorporated herein by reference.

One embodiment of the present invention relates to new or improved battery separators, batteries, systems, components, compositions, and/or methods of manufacture and/or use. One embodiment of the present invention is a new, improved, unique, and/or complex performance battery separator, lead acid battery separator, open lead acid battery separator, reinforced open lead acid battery separator, ISS or micro-hybrid battery separator, ISS open type A lead-acid battery separator, an ISS reinforced open lead-acid battery separator, a battery comprising such a separator, or a system or vehicle comprising such a battery or separator, and/or a manufacturing method, and/or a method of use.

In order to reduce fuel consumption and generation of exhaust gases, automobile manufacturers have changed the stage of electric hybridization (see Fig. 1). One type of hybrid electric vehicle (HEV) is often referred to as a micro HEV. In this micro HEV or concept, the car has an idle stop/start (ISS) function and often a regenerative rotation function. To reduce costs, many automakers are considering flooded lead acid batteries that meet the electrical functionality associated with ISS functionality. Since the functions associated with this battery are somewhat different from standard automotive applications such as SLI (Starting Lighting and Ignition) batteries, differentiation of the functions of the ISS vehicle battery separator and the ISS vehicle battery or improvement in performance can be obtained.

ISS open lead acid batteries can operate in a partial state of charge (PSoC) of about 50 to 80%, unlike typical SLI batteries that operate at 100% charge. With regenerative rotation and frequent restarts, the battery will experience a shallow charge and recharge cycle. Depending on the design of the electrical system, the ISS vehicle battery will not normally overcharge, which will not produce oxygen and hydrogen gases that can be used for acid mixing.

Although the choice of ISS vehicle battery is an ISS or reinforced open lead acid battery, the ISS vehicle battery can be a gel, polymer or other battery, capacitor, supercapacitor, accumulator, battery/capacitor combination, and the like.

The advent of micro HEVs and ISSs with or without regenerative rotation sets new demands for batteries and battery separators. That is, new or improved battery separators, batteries, systems, components, compositions, and/or manufacturing methods and/or methods of use; New, improved, unique, and/or complex performance battery separators, lead acid battery separators, open lead acid battery separators, reinforced open lead acid battery separators, ISS or micro-hybrid battery separators, ISS open lead acid battery separators, ISS reinforced open lead acid There is a need for a battery separator, a battery including such a separator, a system or vehicle including such a battery or separator, and/or a manufacturing method, and/or a method of use.

Inorganic, that is, a group of mineral compounds is known to effectively bind heavy metals such as lead, cadmium, iron, zinc and copper. The mechanism by which minerals bind heavy metals is referred to as PIMS (Phosphate Induced Metal Stabilization), and is widely used for environmental restoration of heavy metals from contaminated soil and water. In environmental remedial applications, large amounts of minerals that process PIMS affinity for toxic metals to reduce heavy metal contamination may be mixed with contaminated soil or contaminated water may be contained within a housing that passes through a bulk PIMS mineral cake.

A common type of failure in the lead acid or lead-calcium battery industry is a "hydration short" phenomenon. This type of short circuit is common in batteries that stay at very low acid concentrations, ie low charge, for long periods of time. In the charged state, the acid density is high, for example, 1.28 g/cm ³ , and the solubility of lead sulfate is low. At low charge, the acid density decreases and the solubility of lead sulfate increases. At low charge, lead sulfate (PbSO ₄ ) enters the electrolyte solution (sulfuric acid H ₂ SO ₄ ) from the electrode plate. Once refilled, lead sulfate precipitates and can form a layer beneath many separator pores. At this time, the pores of the separator are larger than the ionic radii of lead and sulfuric acid. After further recharging of the battery and contact with the negative electrode of the battery, the precipitated lead sulfate can be reduced to lead, and thousands of micro shorts between the electrodes can occur. That is, a hydration short and battery failure may occur.

Typically, this "hydration short" can occur during slow discharge, such as when the battery is stored for long periods of time without maintaining its charge. The traditional approach to avoiding hydration shorts is to add sodium sulfate (Na ₂ SO ₄ ) as an electrolyte solution during battery production. This approach requires an additional manufacturing process that adds sodium sulfate to the electrolyte, and increases the complexity of battery production. The addition of sodium sulfate acts to "block" hydration shorts through a common ion effect, but does not solve the problem of soluble lead formation.

As such, there is a need to address, reduce or eliminate the “hydration short” phenomenon of lead-acid batteries and/or specific applications, such as new or improved battery separators for specific battery applications.

According to one embodiment of the present invention, a new or improved battery separator, battery, system, component, composition, and/or method of manufacture and/or method of use: a new, improved, unique, and/or complex performance Battery separators, lead acid battery separators, open lead acid battery separators, reinforced open lead acid battery separators, ISS or micro-hybrid battery separators, ISS open lead acid battery separators, ISS reinforced open lead acid battery separators, batteries containing such separators, such batteries or separators It relates to a system or vehicle including a, and/or a manufacturing method, and/or a method of use.

Although the preferred battery embodiment of the present invention is an ISS open lead-acid battery, it can be understood that the battery is a gel, polymer or other battery, capacitor, supercapacitor, accumulator, battery/capacitor combination, and the like.

In addition, although the improved separator according to an embodiment of the present invention is a special application in a battery for an ISS vehicle, it can be used for other batteries or devices.

The advent of micro HEVs and ISSs with or without regenerative rotation sets new demands for batteries and battery separators (see Fig. 2). These new requirements can be satisfied by at least some embodiments of the battery or separator of the present invention.

*ISS open lead-acid batteries can operate in a Partial State of Charge (PSoC) of about 50 to 80%, unlike typical SLI batteries that operate at 100% charge. With regenerative rotation and frequent restarts, the battery will experience a shallow charge and recharge cycle. Depending on the design of the electrical system, the ISS vehicle battery will not normally overcharge, which will not produce oxygen and hydrogen gases that can be used for acid mixing.

The above-described new yoke according to an embodiment of the present invention can lead to special and possibly desirable modifications to separators, batteries and/or electrical systems:

1) Charge acceptance/power transfer-Lead-acid batteries are an excellent storage medium for energy, but they have limitations in their ability to accept fast charging when the battery is in a high state of charge. In ISS applications, fast charging can be obtained from the use of regenerative rotation and will recover a large amount of energy used to slow down the vehicle. For this reason, the battery will generally operate at a low charge state. The battery separator will also contribute to the battery's ability to accommodate fast charging. Below are some preferred modifications to the separator to increase charge acceptance/power transfer.

a. Low Electrical Resistance (ER)-In order to maximize power transfer upon restart of the internal combustion engine and charge acceptance during regenerative rotation, it is important to minimize the separator ER. The separator ER can be lowered through the following method:

I. Lower Back-Web (BW) Thickness-Since BW thickness is the main factor in the separator ER, it can be reduced from typical values of 150 to 250 microns. However, due to this, the material may be difficult to apply in a typical packaging process. Here, a method of lowering the BW thickness to 75 to 150 microns and enhancing transversal stiffness using negative cross ribs is recommended (see Figs. 5 and 6).

Ii) Increased silica to polymer ratio-A second way to reduce the separator ER is to increase the loading of silica on the polymer content. A possible major issue with this change is that the oxidation resistance of the separator can be reduced by several steps. In a standard SLI battery, the battery is subject to severe overcharge, and the oxide paper is produced on the positive plate. However, in ISS applications, since the overcharge situation is limited by the design of the electrical system, the battery will not produce oxidizing species, and the separator will not require as much oxidation resistance as required in typical SLI applications. The ratio of silica to polymer can be from 3.0/1.0 to 5.0/1.0.

Iii. Use of High Oil Absorption Silica-A third approach to reducing ER is to use silica which has a high surface area (eg >200 g/m2), which results in high oil absorption. With this type of silica, the amount of pore former in the injection process can be increased from 60 to 65% by weight to 70 to 80% by weight, and a significantly higher final porosity and lowered electrical resistance can be obtained (Fig. 11).

b. Minimize Gas Entrapment-It is recognized that hydrogen and oxygen generated by battery active materials during charging and discharging are trapped by the separator, insulating part of the plate, making it unusable for charging and discharging reactions. . This can be a huge limitation on the battery's ability to accommodate charge and deliver power. The following are special changes to reduce the chances of gas capture:

I. Laminate Structure-In many designs proposed for ISS vehicle batteries, the laminate structure is incorporated into the separator to hold the positive active material (PAM) in the positive plate. In general, such laminates tend to increase the amount of gas trapped within the cell (see Figures 12 and 13). By modifying the laminate structure, gas entrapment can be significantly reduced. Possible preferred variations are as follows:

1. Treating the laminate with chemicals or plasma to change the surface energy of shedding gas bubbles.

2. Perforated to allow bubbles to agglomerate and escape the laminate matrix

3. Addition of nucleating agent

4. Change of laminate structure during formation

5. Addition of polymer fiber to laminate structure

6. Addition of wetting agent

7. Reorient the laminate's fiber structure so that gas bubbles are less adherent to the structure

8. Minimize the thickness of the structure to reduce the space for bubble attachment

Ii. Wetting Agent Selection-It has been demonstrated that the choice of wetting agent for use in polyethylene separators can have a great influence on the stagnation of gas bubbles in the cell. Wetting agents having high hydrophobic properties may exhibit greater performance in this respect than wetting agents having a hydrophilic tendency. For example, ethoxylated fatty alcohols are generally preferred over substituted sulfosuccinates.

Iii. Cross ribs (negative and/or positive)-In tests performed to test gas properties, small negative cross ribs aid in nucleation and/or allow the gas to escape between the plates, reducing the likelihood of gas trapping. It has been shown to aid in the transfer of gas bubbles to the outside.

Iv. Nucleation of gas-various modifications can be made to the separator to help provide a region on the separator that acts as a nucleation site so that gas bubbles can be released from the separator and move between plates to grow quickly and efficiently.

1. Shape-By including nanostructures on the surface of the polyethylene separator, gas nucleation can be significantly increased. Such a nanostructure may be, for example, a pyramid, a chevron or a cylindrical shape. They can be formed by calendering, laser ablation or controlled chemical oxidation.

2. Additives-Additives may be incorporated into the matrix of the separator to provide areas on the surface that change the surface structure or energy. This change can promote the nucleation of small gas bubbles created in critical volumes. Examples of these additives are carbon fiber, carbon nanotubes, or barium sulfate.

2) Hydration Short-This type of short circuit is formed in batteries that stay at very low acid concentrations for long periods of time. This phenomenon is well known in the battery industry, and sodium sulfate in the electrolyte could be used as a potential remedy for this phenomenon. It is believed that in ISS applications where the battery rarely accepts a full charge, the risk of a hydration short is much greater than in a typical SLI battery. Here are some membrane modifications that can reduce the incidence of hydration shorts:

a. Common Ion Effect-It is known that the addition of sodium sulfate to the battery electrolyte prevents the formation of hydration shorts through the common ionic effect. In this variant, sodium sulfate is included in the separator matrix and/or laminate, allowing the sodium sulfate to effectively reduce the chance of formation of a hydration short at the appropriate location.

b. Heavy metal removal-By irreversibly absorbing and removing lead ions in the solution, additives may be included in the separator to prevent formation of hydration shorts. Examples of materials that can be used for this include apatite, zeolite, lignin and rubber derivatives.

c. The site-common ionic effect of the additive or the additive for the removal of heavy metals may be added directly to the matrix of the separator, coated or included in the laminate structure, or coated on the container of the battery case before and after the injection molding process.

d. If a low acid desorption-separator can lower acid desorption, the total amount of sulfate ions in the acid solution will be higher, and will inhibit the hydration effect. In other words, it may be an additional buffer against over-discharging of the battery. To this end, possible preferred modifications to the separator may include low backweb thickness, high porosity or low rib mass of the separator as previously described.

I. Serrated/walled rib-toothed or walled rib designs can be used for low mass of ribs. This concept may be included in detail in US Pat. No. 7,094,498. By modifying the rib design in this way, the separator will have less acid escape.

3) Improved Life-In order to meet the expectations of battery and vehicle manufacturers, especially when the battery is subject to high temperatures and high usage rates, the life of a typical lead acid battery should be improved. In order to reduce the amount of continuous corrosion and overcharge of the positive plate, the state of charge of the battery can be reduced. However, in this case, the probability of hydration shock increases significantly. By modifying the separator, this potential issue can be eliminated. Some potential preferred variations are described below.

a. Laminate-In many deep cycle lead acid batteries, the laminate is used to maintain a positive active mass in a positive grid. This structure was eventually incorporated into the positive plate due to the natural expansion of the positive active mass during the cycling operation. This allows the positive active mass to be kept in close proximity, thereby keeping it for a significantly longer period of time as possible. Separators for open ISS applications include laminates, and the expected duty cycle and environment are expected to be harsh.

I. Glass Mat-In many open lead acid batteries, a glass mat is used to keep the positive active material and the positive grid closely. One potential variant for the ISS will keep the use of a glass mat, and, although potential, mix different fiber lengths and widths in the mat with a compression thickness of 0.1mm to 1.0mm.

*Ii. Synthetic nonwoven-nonwoven polymeric mats have also been used as active material retention in lead acid batteries. These materials are generally made of polyester (meaning the polymat published in US 2006/0141350 A1).

Iii. The hybrid of the glass mixed with the hybrid-polymer can be included in the hybrid mat, which has the stiffness and oxidation resistance of the glass and the tear resistance and toughness of the nonwoven fabric. By combining the properties of both materials, mats for batteries with superior properties can be produced.

b. Profile Selection-The choice of a profile or living design is not considered to add an advantage to a typical open lead acid battery. However, in ISS applications, it is believed that the profile design can have a significant impact on battery performance. The goal of lowering the acid deviation can be achieved with a profile design (see Fig. 26). Conversely, a tighter rib space is advantageous for deep cycle applications. A compromise between the two is required.

4) Acid stratification-In various open lead acid batteries, stratification of acids in electrolytes has been an issue in applications where high cycling requirements and complete recharge are not achieved. When the battery cycle is not repeatedly fully charged or overcharged, the acid of the battery may be separated into areas where water at the top of the battery and sulfuric acid at the bottom are concentrated. In general, the battery manufacturer will specify that the battery should be overcharged in a few steps while promoting electrolysis of water. The hydrogen and oxygen produced during overcharging will stir the electrolyte while mixing the water and acid. As mentioned earlier, in ISS applications, the battery will be kept in PSoC with an acid mix to avoid overcharging. Therefore, the potential advantage of acid mixing or delaying acid stratification from the separator is important.

a. Profile Selection-As mentioned earlier, profile selection is an important attribute for many properties. Another advantage is the inclusion of horizontal ribs against the surface of the separator to act as a physical barrier against acid stratification. The cross ribs can be of a variety of shapes (see previously mentioned negative cross rib patent application and positive cross rib patent).

b. Laminate structure-The laminate structure attached to the polyethylene separator may act to prevent acid stratification. By arranging the fibers in a pattern that traverses and passes the material, the glass mat can prevent the acid from stratifying.

c. Minimizing the surface area-acid stratification may be achieved by increasing the surface area of the separator structure. This can be achieved by reducing the fiber radius of the laminate structure or by increasing the inner surface of the separator using the concentration or type of silica.

5) VRLA-VRLA (Valve-Regulated Lead Acid) batteries are recognized as playing an important role in the market for automotive ISS applications. In this type, the electrolyte is absorbed and held in the matrix of the separator. The main technology for this is to use an absorbent glass mat (AGM) separator, or to gelate silica and electrolyte as a binding agent. Some new approaches to VRLA are reviewed in detail below.

a. Acid Jellifying Separator-Acid Jellifying Separator (AJS) is a concept that has been used in the past. By incorporating a high content of silica with a high surface area in the polyethylene separator, new or improved products are made to sufficiently absorb acid so that the separator is applicable to VRLA design. Daramic AJS products enable manufacturers to use standard open battery architecture equipment and technologies to produce VRLA products. The AJS separator has excellent characteristics in improving cycling and is in close contact with the positive electrode plate, so that shedding of the active material can be prevented. The silica and polymer matrix will prevent electrolyte flow and separation, thus avoiding acid stratification issues.

b. One limiting factor in reducing plate space for batteries containing polyethylene/absorbent glass mat hybrid-AGM separators is the AGM's ability to prevent the occurrence of plate defects and short circuits. In general, short circuits do not appear until the battery is fully assembled and charged, increasing the cost of the product. By including a flat PE separator on or within one side of the AGN separator, the plate space in the battery can be reduced without increasing the initial error. The PE separator will act as a protective film, reducing the likelihood that a small defect in the plate will cause a short circuit.

c. Other laminate hybrids-other laminate systems, nonwovens or other glass mats can be used with a flat PE separator to make an acceptable VRLA separator.

Lead-acid storage batteries not only provide power as the primary power source for electric vehicles, but also for initiating and recovering regenerative current for hybrid electric vehicles, simplified hybrid vehicles, and ISS-compatible vehicles with idle stop and start (ISS) functions. It is required to provide new functions with power.

US Patent Application No. 61/253,096 “LEAD ACID BATTERY SEPARATORS WITH CROSS RIBS AND RELATED METHODS” filed on October 20, 2009 and US Patent Application No. 12/904, 371 “BATTERY SEPARATORS” filed on October 14, 2010 Descriptions and drawings of various modifications and methods of a separator having negative cross ribs of “With CROSS RIBS AND RELATED METHODS” may be included herein by reference.

One embodiment of the present invention relates to new or improved battery separators, specific battery applications, specific uses, etc. that reduce or eliminate the "hydration short" phenomenon of lead acid batteries.

One embodiment of the present invention relates to new or improved batteries, separators, components and/or compositions having heavy metal removal capabilities, and/or methods of making and/or using them; Lead-acid battery components such as new or improved lead-acid batteries with heavy metal removal, single or multi-layer lead-acid battery separators, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrode formulations, electrolytes, etc. Or polymer or resin compositions and/or methods of making and/or using them; New or improved lead-acid batteries, single or multi-layer lead-acid battery separators, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers with heavy metal removal and using at least one PIMS mineral as at least one filler component , Electrode formulations, lead acid battery components such as electrolytes and/or polymer or resin compositions; PIMS minerals, preferably ground fish mills, bio-mineral silica-filled lead-acid battery separators, preferably silica-filled lead-acid battery separators provided as at least some substitutes for the silica filler component in the polyethylene/silica separator formulation, etc. Is provided.

According to one embodiment of the present invention, the present invention provides a new or improved battery, separator, battery casing, battery part, porosity with heavy metal removal ability using a raw material of natural or synthetic hydroxyapatite having heavy metal binding ability such as PIMS mineral. Components such as bags, laminates, coatings, surfaces, fillers, electrode formulations, electrolytes, and/or compositions, and/or methods of making and/or using them.

According to an embodiment of the present invention, a new concept of using PIMS minerals as a filler component in a microporous lead-acid battery separator is provided. According to a possible preferred embodiment, PIMS minerals, preferably fish meals, bio-minerals are at least a silica filler component in a silica-filled lead acid battery separator of the day, preferably a polyolefin/silica or polyethylene/silica/oil separator formulation. It is provided with some substitutions.

According to one embodiment of the present invention, various PIMS (Phosphate Induced Metal Stabilization) have been identified, some of which have been proven to have lead affinity. Fishbone derived PIMS minerals, such as commercial and laboratory ground fish meals, showed very high lead ion affinity compared to other samples. Fish bone powder was extracted in a typical lead acid battery separator format through pilot operation at several loading concentrations. These PIMS-containing membranes were evaluated to have lead removal performance and proved to significantly reduce lead concentration in acidic solutions. For example, a% Pb reduction of about 17% to 100% has been demonstrated. According to one embodiment of the present invention, the fishbone powder replaces a portion of the silica filler with a substitution level of 1% to 20%, more preferably 2% to 10%, most preferably 2% to 5% of the silica. Can be added to According to one embodiment of the present invention, ground fish bone powder, i.e. ground fish mil, is substituted by about 1% to 50%, more preferably about 5% to 30%, most preferably 10% to 20% of the silica. Level can be added to replace some of the silica filler.

The bio-minerals of battery separators are commercially available as extruded polyolefin polymer resins and porous polymer films or membranes.

According to an embodiment of the present invention, lead reduction can be achieved by including PIMS minerals, preferably PIMS minerals derived from fishbone, in a lead-acid battery separator.

The present invention provides new or improved microporous membrane substrates that are chemically active. A wide range of chemically active or reactive mineral fillers are applicable to membrane injection and extraction processes. These minerals are available at low cost with the desired level of purity, and fishbones are industrial wastes available from a variety of sources. As well as simplifying the battery manufacturing process containing sodium sulfate, the low cost of raw materials is an advantage.

A preferred separator of the present invention is, for example, a microporous material having pores of 1 micron or less. However, other materials that are porous or macroporous may also be considered. For example, a macroporous separator having a void greater than 1 micron may include a separator made from rubber, PVC, synthetic wood pulp (SWP), glass fiber, cellulose fiber, polypropylene, and combinations thereof.

According to one embodiment of the present invention, other components and/or compositions and/or methods of manufacturing and/or methods of using them having heavy metal removal capability are provided. According to a preferred embodiment of the present invention, new or improved battery components with heavy metal removal capability, e.g. battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrodes, electrolytes, etc. and/or polymers. Or to a resin composition and/or a method of making and/or a method of using them. According to a preferred embodiment of the present invention, the present invention provides a new or improved lead-acid battery component using at least one PIMS mineral as at least one filler component, e.g., battery casing, battery part, porous bag, laminate, coating. , Surfaces, fillers, electrodes, electrolytes, etc. and/or polymer or resin compositions. In one embodiment, PIMS mineral, preferably ground fish mill, bio-mineral is a silica-filled polymer composition, such as a polyolefin/silica composition, for example a polyethylene/silica/oil formulation suitable for slot die extrusion. Is provided as at least some substituents for the silica filler component.

According to another embodiment of the present invention, new or improved batteries, separators, components and/or compositions having lead removal, bonding, bonding, absorption, retention and/or scavenging capabilities, their manufacturing methods and/or their use methods. About.

1 to 33 are slides, pictures, texts, charts and/or images, respectively, and represent a part of the present application. For example, FIGS. 5, 26, 27 and 32 show a separator of a preferred embodiment.

According to one object of the present invention, a new or improved battery, separator, component and/or composition and/or method of manufacture and/or method of use having heavy metal removal capability; Lead-acid battery components and/or polymers such as new or improved lead-acid batteries with heavy metal removal capability, single or multiple layers of lead-acid battery separators, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrodes, electrolytes, etc. Or a resin composition and/or a method of making and/or using the same; A new or improved lead-acid battery containing at least one PIMS mineral as at least one filler component, using at least one raw material of natural and/or synthetic hydroxyapatite having heavy metal removal ability and heavy metal binding ability, single Or lead-acid battery components such as multiple layers of lead-acid battery separators, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrodes, electrolytes, and/or polymer or resin compositions; A microporous lead-acid battery separator provided to partially replace the silica filler component of a PIMS mineral, preferably fish meal, a silica-filled lead acid battery separator, preferably a polyethylene/silica separator formulation; A battery separator, a method of manufacturing a battery separator, a method of using a battery separator, an improved battery separator, and/or an improved separator or laminate for lead-acid batteries, and the like are provided.

1 to 33 are slides, pictures, texts, charts and/or images, respectively, and represent a part of the present application. For example, FIGS. 5, 26, 27 and 32 show a separator of a preferred embodiment.

According to one embodiment of the present invention, a new or improved battery separator, battery, system, component, composition, and/or method of manufacture and/or method of use; New, improved, unique and/or complex performance battery separators, lead acid battery separators, open lead acid battery separators, reinforced open lead acid battery separators, ISS vehicle or microhybrid battery separators, ISS vehicle open lead acid battery separators, ISS vehicle enhanced open type A lead acid battery separator, a battery including such a separator, a system or vehicle including such a battery or separator, and/or a manufacturing method, and/or a method of use, and the like are provided.

The separator, battery and/or electrical system according to an embodiment of the present invention preferably includes at least one, more preferably at least two, and most preferably at least three of the following improvements, features, changes, modifications, enhancements, performance, Features, Profiles, Shapes, Settings, Structures, Parts, Attributes, Spaces, Thicknesses, Ratios, Blends, Blends, Formulations, Additives, Auxiliaries, Coatings, Layers, Laminates, Mats, Nonwovens, Surfaces, Inclusions, Effects, Sun, Conduct Examples include combinations, subcombinations, etc.

1) Charge acceptance/power delivery-preferred features or modifications to the separator to increase charge acceptance/power delivery:

a. Low or Lower Electrical Resistance (ER)-In order to maximize charge acceptance during regenerative rotation and power transfer when the internal combustion engine restarts, it is important to minimize the membrane ER. The membrane ER can be lowered by the following method:

I. Lower backweb (BW) thickness-Since BW thickness is the main contributor to the separator ER, it can be reduced from typical values of 150 to 250 microns. However, at this time, the material is very difficult to apply to a typical packaging process. Here, a method of lowering the BW thickness between 75 and 150 microns and using negative cross ribs (see FIGS. 5 and 6) to enhance the transverse rigidity is recommended.

Ii. Increasing the silica to polymer ratio-A second way to reduce the ER of the separator is to increase the content of silica relative to the amount of polymer. One possible important issue with this change is that the oxidation resistance of the separator can deteriorate in several steps. In standard SLI batteries, the battery is subject to overcharging, and the oxide paper is formed on the positive plate. However, in ISS automotive applications, since the overcharge situation is limited by the design of the electrical system, the battery will not generate oxidizing species and the separator will not be required to have as much oxidation resistance as required in typical SLI applications. The silica to polymer ratio can vary from about 3.0/1.0 to 5.0/1.0.

Iii. Use of silica having a high surface area by increasing high oil absorption and porosity-A third method to reduce the ER of the separator is to use silica having a high oil absorption rate and a high surface area (eg >200 g/m2). With this silica, the amount of the pore former in the injection process can be increased from 60 to 65% by weight to 70 to 80% by weight, and very high final porosity and low electrical resistance can be obtained (see Fig. 11).

b. Minimizing Gas Entrapment-It is known that hydrogen and oxygen produced by the battery active material during charging and discharging are captured by the separator, insulate part of the plate and render it unusable for charging and discharging reactions. This can be a huge limitation on the battery's ability to accept charge and deliver power. The following are several changes that reduce the chances for gas capture:

I. Laminate Structures and Modifications In many designs proposed for ISS vehicle batteries, the laminate structure has been incorporated into the separator to hold the positive active material (PAM) in the positive plate. In general, such laminates tend to increase the amount of gas trapped within the cell (see Figures 12 and 13). By modifying the laminate structure, gas entrapment can be significantly reduced. Potentially desirable variations are:

1. Treat the laminate with a plasma or chemical that changes the surface energy to shedding gas bubbles

2. Perforated to allow bubbles to agglomerate and exit the laminate matrix

3. Addition of nucleating agent

4. Change of laminate structure during formation

5. Addition of polymer fibers and/or deformed polymer fibers to the laminate structure

6. Addition of wetting agent (surfactant)

7. Reorient the laminate's fiber structure to minimize gas bubbles from reaching the structure.

8. Minimize the thickness of the structure to reduce the area for bubble adsorption.

Ii. Wetting Agent Selection-It has been demonstrated that the selection of a wetting agent for use in polyethylene separators can have a great influence on the retention of gas bubbles in the cell. Wetting agents with strong hydrophobic properties may show better performance in this respect than wetting agents tending to be hydrophilic. For example, ethoxylated fatty alcohols may generally be preferred over substituted sulfosuccinates.

Iii. In tests conducted to test negative and/or positive separator cross rib-gas properties, small negative cross ribs aid in nucleation and/or evacuate gas from between the plates, reducing the possibility for gas trapping and outside the cell. It appears to aid in the delivery of gas bubbles.

Iv. Nucleation of Gas-To help provide a region of the membrane that acts as a nucleation site for rapid and efficient growth as gas bubbles exit the membrane and move between the plates, modifications to the membrane can be made.

1. Profile shape (roughness)-By incorporating nanostructures onto the surface of the polyethylene separator, gas nucleation can be significantly increased. Such a nanostructure may be, for example, a pyramid, a V-shape, or a cylindrical shape. They can be formed by calendering, laser ablation or controlled chemical oxidation.

2. Additives-Additives may be included on the surface or matrix of the separator to provide an area on the surface that alters the surface structure or energy. This modification can facilitate nucleation of small gas bubbles created in critical volumes. Examples of such additives are carbon fiber, carbon nanotubes or barium sulfate.

2) Prevention, delay, reduction, elimination of hydration shorts-Such short circuits can be formed in batteries that are maintained at very low acid concentrations for long periods of time. This phenomenon is well known in the battery industry, and sodium sulfate is added as an electrolyte to prevent a hydration short. In ISS applications where the battery is barely full-charged, it is believed that the risk of forming a hydration short is significantly greater than that of a typical SLI battery. The following shows a new membrane change that can reduce the occurrence of hydration shorts:

a. Common Ion Effect-It is known that the addition of sodium sulfate to the battery electrolyte can prevent the formation of hydration shorts due to the common ion effect. In this variant, sodium sulfate is included by impregnation with the separator matrix and/or laminate material, and sodium sulfate at the appropriate location most effectively reduces the chance of hydration formation.

b. Heavy metal removal-By irreversibly absorbing and removing lead ions in the solution, the additive may be included in the separator or on the surface of the separator, in the laminate material, in the electrolyte, in the battery casing, etc. to prevent formation of a hydration short. Examples of materials that can be used for this include apatite, hydroxyapatite material, ground fish meal, zeolite, lignin, latex and rubber derivatives.

c. Site-common ionic effect of additives or additives related to heavy metal removal are added directly to the matrix of the separator, preferably as a substitution filler for a portion of silica, coated on the separator, coated or included on the laminate structure, and implanted It is known that it is coated on the container of the battery case before and after the molding process, and can be placed in a porous bag or bag of an electrolyte or laminate structure.

d. If the lowered or reduced acid release-separation membrane can lower the acid release, the amount of sulfate ions in the acid solution increases, and the hydration effect can be slowed. That is, this may be an additional buffer for over-discharge of the battery. Potentially preferred membrane modifications for this are as follows:

I. Thin backweb-added cross ribs, preferably low backweb (BW) thickness with negative cross ribs as discussed above, high porosity and/or low rib mass of the separator.

Ii. Serrated/walled rib-toothed or walled rib designs may be used to remove mass from the ribs. This concept is described in US Pat. No. 7,094,498, incorporated herein by reference. By modifying the rib design in this way, the separator can have low acid escape.

3) Improving Life-In order to meet the expectations of battery and vehicle manufacturers, the life of a typical lead-acid battery, especially when the battery is applied to high temperature and high duty cycle, should be improved. One idea is to reduce the battery's state of charge to reduce the amount of continuous corrosion and overcharge of the positive plate. However, by doing in this way, the probability of a hydration short greatly increases. By modifying the separator, this potential issue can be eliminated. Some potential preferred variations are described below.

a. Laminate Structure-In many deep cycle lead acid batteries, a laminate is used to maintain a positive active mass in a positive grid. This structure is eventually incorporated into the positive plate due to the natural expansion of the positive active mass during the cycling operation. This allows the positive active mass to remain intimate, thereby maintaining performance for as long as possible. As the expected duty cycle and environment are harsh, it is expected that separators for open ISS automotive applications will include laminates.

I. Glass Mat-In many open lead acid batteries, a glass mat is used to hold the positive active material and the positive grid closely. A preferred variant for the ISS is to continue the use of the glass mat, although mixing various fiber lengths and widths at compressed thicknesses of 0.1 mm to 1.0 mm. Preferably a new or improved separator for open ISS applications will include such a laminate.

Ii. Synthetic nonwoven-nonwoven polymeric mats have recently been used as an active material retainer in lead acid batteries. These materials are generally made of polyester (see Polymat Publication Patent Application, US 2006/0141350 A1, incorporated herein by reference). New or improved separators will preferably include such laminates for open ISS applications.

Iii. A hybrid of the glass mixed with the hybrid-polymer is contained within the hybrid mat, which will have the stiffness and oxidation resistance of the glass along with the tear resistance and toughness of the nonwoven fabric. By combining the characteristics of the two materials, mats with dominant characteristics can be manufactured for batteries. New or improved separators for open ISS applications will preferably include such laminates.

b. Profile Selection-The selection of a profile or living design is not often considered as adding the benefits of a typical open lead acid battery. However, in ISS applications, the profile design is known to have a significant impact on battery performance. The goal of low mountain deviation can be achieved by profile design. Conversely, a tighter rib space can work advantageously for deep cycle applications. A unique compromise between the two may be required. Examples include new or improved profiles with shorter rib heights and tighter rib space, narrower ribs, and rampart ribs.

c. Polyaspartic acid-polyaspartic acid retards crystal formation. According to the present invention, polyaspartic acid is preferably added directly to the matrix of the separator, coated on the separator, coated or included in a laminate structure, coated with a container of a battery case before and after injection molding process, or coated with an electrolyte or a laminate structure. It can be placed within a bag of or a porous bag.

d. Compression-compressible, flexible and/or resilient rib structures can enhance life. For example, an I-beam rib profile can provide the desired compression.

4) Acid Stratification-In a variety of open lead acid batteries, acid stratification in electrolytes has been an issue in heavy cycling demands and in applications where full recharge is not possible. When the battery cycle is repeated without being fully charged or overcharged, the acid in the battery may be separated into a place with water at the top of the battery and a place with a concentration of sulfuric acid at the bottom. In general, the battery manufacturer will specify that the battery promotes the electrolysis of water and must be overcharged in several steps. The hydrogen and oxygen created during this overcharge will stir the electrolyte and mix water and oxygen. As mentioned earlier, in ISS applications, the battery will be maintained in PSoC conditions with little chance of overcharging to mix the acid. Therefore, the potential benefit of acid mixing or delaying acid stratification from the separator can be significant.

a. Profile Selection-As mentioned previously, profile selection can be an important attribute for many features. Another advantage is the inclusion of horizontal ribs across the surface of the separator to act as a physical barrier against acid stratification. Such cross ribs may take a wide range of forms, such as the aforementioned negative cross rib patent application and positive cross rib patent.

b. Laminate Structure-The laminate structure attached to the polyethylene separator may act to prevent acid stratification. By arranging the fibers in a pattern across and through the material, the glass mat can help prevent acid from stratifying. In addition, adding a laminate structure to the positive and negative faces of the polyethylene separator may serve to reduce acid stratification.

c. Minimizing the surface area-acid stratification may be achieved by increasing the surface area of the separator structure. This may be achieved by first reducing the fiber radius of the laminate structure, secondly increasing the inner surface of the separator according to the type or concentration of silica, increasing the porosity, or configuring a cross rib.

d. Acid Immobilization-Minimizing acid stratification can also be achieved by immobilizing acids. This can be achieved by adding a layer of silica to the surface of the laminate and/or separator or adding a layer of silica to the laminate, for example, including cross ribs that tend to keep the acid in place (see Fig. 26), or using Daramic AJS technology. The acid can be'gel'ed and immobilized by adding silica.

5) VRLA-valve regulated lead acid (VRLA) batteries may be important in the market for automotive ISS applications. In this type of structure, the electrolyte is absorbed and held in the matrix of the separator. The dominant technology for this is to use an absorbent glass mat (AGM) separator, or to gel the electrolyte together with silica as a binder. The new approach to VRLA technology is reviewed in detail below.

a. Acid gelation membrane-acid gelation membrane (AJS) is a concept that has been used in the past. A new or improved product was produced by modifying the membrane to contain silica with a high surface area along with a high content of silica in the polyethylene membrane. It has been designed to be sufficiently absorbed. These new Daramic AJS separators could allow manufacturers to use standard open battery rescue equipment and technologies to produce VRLA products. The Daramic AJS separator has excellent characteristics in improving cycling, which prevents storage of active materials and is in close contact with the positive plate. Since the silica and polymer matrix prevent the flow and separation of the electrolyte, this may also prevent acid stratification problems.

b. An important limiting factor in reducing plate space in batteries with polyethylene/absorbent glass mat hybrid-AGM separators is the ability of AGM to overcome plate defects and prevent short circuits from occurring. In general, such a short circuit does not appear until the battery is fully assembled and charged, and thus manufacturing cost may be high. By including a flat PE separator inside or on one side of the AGM separator, the plate space of the battery can be reduced without increasing the initial failure. The PE separator will reduce the likelihood of small plate defects causing a short circuit and will act as a shield.

c. Other laminate hybrids-other laminate systems, nonwovens or other glass mats can be used with flat PE separators to make acceptable VRLA separators.

The creative lead-acid storage battery not only provides power as the main power source for electric vehicles, but also for starting and restoring regenerative current for hybrid electric vehicles, ISS-compatible vehicles and hybrid vehicles with simple idle stop start (ISS) function. It may be required to provide new functions as a power source.

US Patent Application No. 61/253,096, filed Oct. 20, 2009, "LEAD ACID BATTERY SEPARATORS WITH CROSS RIBS AND RELATED METHODS" and Oct. 14, 2010 with respect to various modifications and methods of separators including negative cross ribs. The full description and drawings of US Patent Application No. 12/904,371, filed in "BATTERY SEPARATORS WITH CROSS RIBS AND RELATED METHODS", are hereby fully incorporated by reference.

In order to maintain or improve the performance of the separator, it is proposed here to increase the bending stress of the separator by forming a tightly spaced transverse rib on one side of the separator facing the cathode (see FIGS. 5 and 26). Several tests on commercial envelopes with Daramic Duralife® separators containing negative cross ribs showed a significant improvement in yield compared to standard flat surface separators (see FIG. 25). Increasing the bending stress improves the packaging process, and it can be expected that the electrical resistance of the separator can be reduced by 25% due to the thinner base web or back web (BW) thickness of the separator.

By reducing the thickness of the separator, we expect two benefits in battery performance. First, a 25% lower separator electrical resistance will improve the battery's power delivery and charging capacity. Next, due to the small volume filled by the separator, there may be more acid between the electrodes. Since many batteries are designed with limited electrolytes, replacing the acid and separator mass can be advantageous in terms of the battery's electrical storage capacity.

There are other opinions that increase the amount of acid between the electrodes and lower the separator electrical resistance. Today, a typical PE separator has a porosity of 60%, in other words, 40% of the volume of the separator is occupied by the mass. If we reduce the mass of the separator by half, or 20%, the electrical resistance will decrease by a similar rate, resulting in a separator porosity of 80%. In order to confirm the assumption, experimental separators having various porosities were prepared and the resulting electrical resistance was measured (see FIG. 7).

By using a special type of high surface area silica, the PE separator can have very high porosity and lower electrical resistance. Preferred separators with the lowest electrical resistance can be obtained by combining negative cross ribs with new silica of thin BW thickness and very high porosity.

There are other ways to lower the functional electrical resistance of the separator and improve battery performance. The term'functional' electrical resistance is used deliberately herein and is distinguished from the'measured' electrical resistance of the separator (see FIGS. 8 and 10). Today, membrane electrical resistance is often quantified with devices in which the voltage is applied to a chemical cell through a pair of electrodes. Resistance is measured with and without a separator between electrodes, and this quantifies the electrical resistance of the separator. Although this method allows predicting the effect of the separator on battery performance, there is an important factor missing, namely gas trapping.

When the electrode is charged, during formation or charging, oxygen and hydrogen are made at the positive and negative electrodes respectively. As the electrolyte rapidly becomes saturated with these gases, bubbles are created. As these bubbles form in the electrolyte, they merge into large lumps and rise to the surface of the electrolyte, like carbon dioxide in a freshly poured beer glass. However, the process of discharging the gas is relatively slow, and has a great influence on battery performance. Like a beer mug, these small bubbles adhere to various surfaces including the separator. Bubbles adhere to areas lacking electrolyte, and these areas become areas with high resistance. Therefore, the'functional' electrical resistance of the separator can be described as the measured electrical resistance, and the ratio of the surface area covered by these gas bubbles must be considered.

To measure the captured gas, cells were prepared with standard and modified separators (see Fig. 9). After formation and overcharge, the electrolyte level was recorded for each cell, and a vacuum was induced to release the gas; The level difference is defined as the captured gas. To make the baseline, the cell was tested without a separator; Instead, a glass rod was used to maintain the electrode space. From this work, information on the amount of gas entrapment associated with the electrode was obtained. As can be seen in Table 5 below, adding a standard separator can double the amount of trapped gas compared to a cell without a separator. By using a modified separator, i.e. Daramic Duralife with negative cross ribs, the gas entrapment associated with standard separators can be reduced by about 50%.

[Table 5]

Previously, for an improved packaging process, a separator material having a thinner backweb thickness than those available today was proposed by lowering the separator electrical resistance by adding negative cross ribs. Initially, there was concern that negative cross ribs would increase gas entrapment. It is important to note that the negative cross rib now contains Daramic Duralife which traps less gas than standard separators. It has been demonstrated that the negative cross rib pattern acts as a medium to agglomerate small gas bubbles into larger bubbles, and the buoyancy is greater than the surface adhesion, allowing the gas to escape faster than when using a standard separator.

So far, we have demonstrated a method of lowering the electrical resistance by 25 to 25% compared to a standard separator with two independent actions. Through our tests, we also found a way to reduce the amount of gas trapped on the membrane surface by more than 40% by yielding currency conversion equivalents with functional membrane electrical resistance. Combining these changes, it is expected that the functional resistance can be reduced to a level of 50 to 25% of a typical separator value. This can improve power delivery and charging acceptance in micro hybrid batteries and ISS vehicle batteries.

We proposed that the micro hybrid battery is a hybrid of a high power car battery and a high energy deep cycling battery. Contents to improve the deep cycling behavior required in such applications will be described. If the lead-acid battery is frequently or deeply cycled, the positive active material will be shedding, the negative active material will sulphate, the negative lug will be thin, and the acid is particularly prone to stratification in the partial charge state, and eventually hydration short. Can occur through the separator. Many design options have been studied to address this situation, but we will consider more about the separator. If we can keep the active material in place for a long time, we can extend the functional life of the battery. To avoid shedding of the active material, there are two options: first, to increase the number of ribs on the separator to provide more contact points to keep the positive active material in control; And, next, a laminate such as a glass mat is added to the separator.

The laminate provides a positive support to prevent shedding of the positive active material. However, these laminates must be carefully selected so as not to increase gas entrapment, thereby increasing functional electrical resistance and lowering the battery's power delivery and charging acceptance. Using the previously described methods, a gas entrapment test was performed on a separator comprising various laminates. In the laboratory, we first determined the amount of gas trapped in association with the plates and separators to observe the effects of the various laminates. From the tests we can see a large difference between the various laminates with respect to the level of gas entrapment. Therefore, in order to maintain good charge acceptance and power transfer while maintaining good protection against the shedding of the positive active material, it is necessary to select the correct laminate (see FIGS. 12 and 13).

There are other synergies between cycling and good electrical performance. In our early work, we found a way to increase the electrolyte between the electrodes. This was achieved by lowering the thickness of the back web of the separator, increasing the porosity of the separator, and reducing the amount of gas trapped in the separator. In general, we believe that these steps will prevent hydration shorts, the onset of acid stratification, and sulfation of the cathode. Therefore, we believe that more acid between the plates will improve charge acceptance, power transfer and extend the functional life of batteries used in microhybrid applications.

To this end, we propose a separator concept for battery improvement. In order to improve the battery's power output and charging acceptance, the methods of reducing the electrical resistance of the separator are 1) negative cross ribs that allow a thin separator in the Duralife separator, and 2) significantly increase the porosity of the separator and drastically increase the electrical resistance. Includes ways to reduce. The aforementioned modifications will also act to increase the available acid between the plates, thus increasing the electrical capacity of the battery if the electrolyte is limited. In order to also increase the amount of acid between the plates, we proposed a gas coagulation and migration method that exhibits better electrical performance.

In order to extend the functional performance of lead-acid batteries, especially in deep cycling applications, we proposed to increase the number of ribs to provide more contact points of the positive active material that are prone to shedding during heavy cycling. Another way to prevent shedding of the active material is to add a laminate to the separator. However, these laminates must be carefully selected to minimize the amount of gas trapped and to maximize the battery's power delivery and charging acceptance. The lifespan can be prolonged by preventing a hydration short through the separator or minimizing the onset of acid stratification (see FIG. 14).

We believe that this new concept of microhybrid applications can be applied immediately to products that reflect current market demands. For example, an improved enveloper process will benefit battery manufacturers looking to improve plant efficiency. Variations in separators that improve power and electrical functionality by reducing gas entrapment will benefit battery manufacturers looking to upgrade their current battery ratings.

The present invention is suitable for microporous materials (e.g. pores of 1 micron or less), but other porosities including separators made from rubber, PVC, synthetic wood pulp (SWP), glass fiber, cellulose fiber, polypropylene and combinations thereof It can also be applied to macroporous (eg pores larger than 1 micron) materials.

According to one embodiment of the present invention, an improved, unique, and/or high performance ISS lead-acid battery separator, for example an improved ISS open lead-acid battery separator, an ISS vehicle battery comprising such a separator, a production method and/or Or a method of use is provided. A preferred ISS vehicle battery separator according to an embodiment of the present invention has the characteristics of several separators at the same time and will include negative cross ribs and PIMS minerals.

The present invention is not limited to a separator for an ISS open lead-acid battery, for example, a polyolefin separator, preferably a filled polyethylene separator, and a capacitor, an accumulator, a gel battery, a polymer battery, a carbon battery, a battery/capacitor combination, electrochemical It can also be applied to cells, porous membranes, porous films, porous laminates, coated membranes and separators for their bonding.

According to one embodiment of the present invention, improved, unique, and/or complex performance battery separators, lead acid battery separators, open lead acid battery separators, enhanced open lead acid battery separators, ISS or micro-hybrid battery separators, ISS It relates to an open lead acid battery separator, an ISS enhanced open lead acid battery separator, a battery comprising such a separator, a system or vehicle comprising such a battery or separator, a manufacturing method and/or a method of use.

Since current separator technology deals with one or two important characteristics for an individual separator, a preferred battery separator according to the present invention handles and optimizes several separator characteristics simultaneously. In accordance with this embodiment, the present invention recognizes the need to deal with several separator characteristics simultaneously, selects a specific combination of several separator characteristics, and makes a plurality of characteristic battery separators that are commercially viable as described below. will be.

In order to reduce fuel consumption and exhaust pipe emissions, automobile manufacturers have implemented various stages of electric hybridization. One form of hybrid electric vehicle (HEV) is often referred to as'micro HEV' or'micro-hybrid'. In this micro HEV or concept, the vehicle has an idle stop/start (ISS) function and frequent regeneration rotation. To reduce costs, many automakers are considering open or enhanced open lead acid batteries (EFBs) to meet the electrical functionality associated with ISS functionality. As the functionality for these batteries often differs from standard automotive applications such as Starting Lighting and Ignition (SLI) batteries, this results in improved performance or other features of the ISS or micro-hybrid battery separator.

According to embodiments of the present invention, improved, unique, and/or complex performance battery separators, lead acid battery separators, open lead acid battery separators, reinforced open lead acid battery separators, ISS or micro-hybrid battery separators, ISS open lead acid batteries A separator, an ISS reinforced open lead-acid battery separator, a battery including such a separator, a system or vehicle including such a battery or separator, a method of manufacturing the same, and/or a method of use thereof are provided.

Although one possible embodiment is a vented or flooded lead-acid battery, such batteries are reinforced open lead-acid batteries (EFB), valve-controlled lead-acid (VRLA) batteries, low-retention lead-acid rechargeable batteries, absorbent glass mat (AGM) batteries, VRLA. AGM batteries, gel batteries (gel cells), VRLA gel batteries, sealed lead-acid batteries,'acid-restricted' design batteries, and "recombinant" batteries (oxygen contained in the positive plate recombines with hydrogen that will be contained in the negative plate to remove water. Will make), polymer, carbon lead acid or other batteries, capacitors, supercapacitors, accumulators, battery/capacitor combinations, etc.

In addition, the improved separator of the present invention may be specially applied to batteries for ISS vehicles, ISS systems, and ISS vehicles, or may be used in other batteries or devices.

Micro HEVs and ISSs with or without regenerative rotation create new demands for batteries and battery separators. This new need can be addressed by any of the embodiments of the inventive separator, battery, system or method.

ISS open lead acid batteries will operate at a partial charge state (PSoC) of approximately 50 to 80%, unlike typical SLI batteries that operate at 100% charge. With regenerative rotation and frequent restarts, the battery will experience a shallow charge and recharge cycle. Depending on the design of the electrical system, ISS vehicle batteries will generally not go into an overcharged state, making oxygen and hydrogen gases that can be useful for acid mixing.

Lead-acid batteries continue to grow and expand with new applications. One growing application category is referred to as deep cycling where the battery is discharged frequently and deeply. Examples of such applications include, for example, idle-start-stop, power backup, wind or solar related renewable energy and traction related micro-hybrid vehicles used in power electric fork trucks, golf carts and the like.

Since lead-acid batteries are being used in these deep cycling applications, a lot of work is needed to improve the suitability for use, especially for micro-hybrid vehicles. To this end, scientists are studying various options to improve the conductivity and utilization of the active mass, prevent the harmful effects of sulfation, minimize grid and lug corrosion, and prevent active material shedding (see Fig. 16). . Even though lead-acid batteries have been in commercial use for over 100 years, they are still improving.

According to one embodiment of the present invention, new, improved, high performance, and/or complex performance separators can have a positive impact to broaden the functionality of lead acid batteries in such deep cycle applications. As the battery industry grows, in recent years, many studies have focused on the development of separators for micro-hybrid vehicles, but these advances are believed to be beneficial to the widening deep cycling market. To provide contextual information, we start with the historic achievements made in the membrane design and conclude with recent work or work in progress.

As shown in FIG. 17, historically, lead-acid batteries used a separator made of wood chips, rubber, sintered PVC, and impregnated cellulose material. As separators, these materials are declining worldwide for a variety of reasons. Referring to Figures 18 and 19, we focus on some of the properties found in new separators that fundamentally replace the old technology: 1) pore size distribution, 2) acid escape, 3) redox, and 4) Weldability. In order to understand the importance of the pore size of the separator, we must first know that the lead particles used in the active material have an average radius of 1 to 5 microns. In order to prevent the movement of lead particles through the separator and thereby prevent the formation of points of electrical conductivity between the electrodes, there has been a transition from a historical separator material to a separator material with submicron pores such as a PE separator.

The next issue is acid escape, suggesting the volume occupied by the separator. The larger the volume occupied by the separator, the less acid is available between the electrodes. In general, a low separator volume and a large amount of acid increase battery capacity, and particularly, when limited by the acid volume in the battery, can increase the discharge rate. Since the new separator material occupies a smaller volume than before, more oxidation resistance is required to perform its function through a predetermined lifetime. Briefly, separators that allow more acid between the plates typically have a thinner backweb thickness, which needs to withstand oxidative attack better.

The last point of historical interest is the ability to be formed into a pocket or sleeve. Often, the functional life of a lead acid battery can end abruptly due to mossing, side or bottom shorts. By mossing, even in the presence of mudroom, we mean that the active material is sheathed and a conductive bridge is formed around the side or below the separator. Separators, which can be made into pockets or sleeves, can greatly reduce or prevent this type of failure.

So far, we have talked about the most basic function of a separator that separates the anode and the cathode while allowing free flow of ions and electrolytes. Referring to FIG. 20, we see the active function of the separator, hiding what is often called antimony poisoning. During the life of the battery, some of the antimony added to the positive grid will dissolve in the electrolyte and migrate and deposit on the surface of the negative electrode. Precipitation of antimony depolarizes the cathode, which causes a greater voltage to be loaded on the anode during charging. When the battery is charged, the antimony that precipitates at the negative electrode will accelerate the hydrolysis of the water before the lead sulfate is converted back to sponge lead. Therefore, some of the charging current will not be stored and will be consumed to make hydrogen and oxygen from water.

For this antimony issue, battery manufacturers have either reduced the concentration of antimony or eliminated it completely. However, in deep cycle applications, there are many advantages of alloying with antimony (see Figure 21). When the battery is deeply discharged, the lead is converted to lead sulfate with a volume increase of about 40%, which leads to expansion in the cell. Antimony alloys increase the strength of the grid, prevent harmful deformation and can help convert lead sulfate back to lead during charging. Next, it is known from experience that antimony alloys improve the interface between the active material and the grid. With the improved interface, useful applications of the active material and improved filling acceptance can be expected. The most important reason for antimony is to reduce or delay the corrosion rate of the positive grid. Without revealing any previous work in the field of metallurgy, antimony alloys are one typical design change to lower grid corrosion in frequently discharged batteries.

According to an embodiment of the present invention, battery manufacturers can take advantage of the aforementioned advantages related to antimony, and harmful effects can be solved by selecting an appropriate separator. Suitable or preferred separators are modified, new, improved, and/or complex performance PE separators. PE separators have been used for years in deep cycling applications such as motive power, inverter batteries, golf carts and SLI applications with stringent OEM specifications for renewable energy and even low water loss. Therefore, when using an antimony alloy, it is important to select an appropriate separator that takes full advantage of its advantages and eliminates the associated detrimental effects.

As previously indicated, many scientists in the field of lead-acid batteries have focused heavily on meeting the needs of ISS or micro-hybrid vehicles. Referring to FIG. 22, the demands of ISS or micro-hybrid applications include high power requirements for SLI batteries and deep cycling requirements for motive power applications.

We start by looking at variations on the separator for the high power of batteries. When the internal resistance is lowered, more power can be obtained from the battery. By providing more acid between the electrodes, diffusion-related limitations can be solved, and more power can be obtained. Membrane resistance is often characterized outside the battery in laboratory equipment. While values derived from these devices are generally useful, we believe there is a significant element loss, i.e. gas entrapment (see Fig. 23). In open lead-acid batteries, gases are produced in different classes depending on the charging current. These gases will eventually leave the battery, but will adhere to the electrode and separator surfaces for a while. When the gas is attached, it becomes a dead zone for ion conduction. We have found a way to efficiently reduce the amount of gas adhering to the membrane by about 40%. By reducing the gas for the separator to preferably 40% or more, a significant improvement in the functional ionic resistance for the separator will improve the power performance of the battery.

Another way to improve the power of the battery is to increase the amount of acid between the electrodes (see Fig. 24). According to one embodiment of the present invention, this is done through stepwise modification of the separator. First, the oxidation resistance of the separator is reduced, so that the mass of the separator is reduced without reducing the fundamental function of the separator, and there is a need for improvement to prevent an electrical short of the electrode. With the reduced mass, the separator must still have adequate mechanical properties to be assembled into the battery. These two characteristics are hole resistance and bending stiffness. By improving the oxidation resistance while maintaining an appropriate level of pore resistance and stiffness, the separator mass can be reduced to increase the volume of electrolyte between the electrodes. With more acids available between the electrodes, the battery faces less problems with acid diffusion, thereby improving power output. The table in FIG. 24 shows the results of comparing selected standard Daramic® HP and DuraLife® separators, provided by North Carolina, LLC Ab Charlotte, and Daramic for micro-hybrid battery applications.

Comparing the two membranes, we can see that the DuraLife® separator demonstrates a large increase in oxidation resistance, while maintaining the high pore resistance found in Daramic® HP, and lowers the mass by about 15%. The low mass of the separator may mean a low acid replaced by the DuraLife® separator and thus a large amount of acid between the plates. Manufacturers focused on micro-hybrid applications are looking for batteries that include Daramic DuraLife® separators that have low battery resistance and high power output during fast discharge compared to standard PE separators.

Another major challenge for microhybrid applications is the ability to extend the life of the battery. In these applications, the battery often operates on a partial charge, and is discharged to varying degrees depending on the amount of electrical duty while the vehicle is stopped and not fully recharged between discharges.

In addition to releasing power quickly to restart the engine after various stops, the battery can also experience tens of thousands of shallow cycles over the expected life of the battery. When such a battery is cycled, there is an opportunity to generate an acid gradient (see Fig. 25). If the acid is concentrated at the bottom of the cell, the electrochemical reaction will be further restricted to the top of the electrode, which will lead to an inexperienced capacity loss. In deep cycle applications, sufficient overcharging will create gas bubbles that will help prevent acid mixing and acid stratification. However, in applications where the battery is hardly fully charged, such as ISS, other measures have to be applied to prevent acid stratification.

In order to use other means to prevent acid stratification, it is important to first understand the mechanism. When current is applied to the battery in a partially charged state, the lead sulfate is converted and a high concentration of sulfuric acid is initially formed on the plate surface. In this example, a boundary layer of sulfuric acid will be formed adjacent to the plate surface. Since this acid layer is more concentrated than the bulk acid, there will be a driving force to mix or diffuse the lower concentration of acid in the bulk space. In addition to the diffusion forces, gravity may be active in these boundary layers. Unfortunately, highly concentrated sulfuric acid is 10 to 20% heavier than bulk acid, and this boundary layer will act like a dense column and will concentrate the acid at the bottom of the cell. This trend towards acid stratification is found especially in open batteries operating in partial charge states where the acid is not fixed by the separator. Upon charging in a VRLA battery, the concentrated acid produced on the electrode surface immediately contacts the glass fibers that fill the entire space between the electrodes, and the capillary action across the fibers provides resistance to gravity, reducing the tendency to stratify the acid.

With the introduction of the DuraLife separator, there are design changes that are believed to reduce acid stratification in open lead-acid batteries and that actual battery tests are convinced of positive results. First of all, DuraLife membranes occupy about 15% less volume than traditional membranes. Therefore, more acid is available between the electrodes, which is important to maximize electrical performance. The next design parameter to be aware of is preferably a negative cross rib structure (see Fig. 26). In general, the surface of the separator facing the cathode is flat or has mini-ribs in a vertical or vertical direction (see FIG. 25).

Referring again to FIG. 26, the preferred negative cross rib design in connection with the DuraLife separator has a number of small mini ribs in the horizontal or transverse direction. It is believed that the electrolyte is fixed at the same level as there are many small mini ribs in the horizontal direction (see Figure 26). These negative cross ribs provide mechanical barrier differences and similarities to the AGM membrane's ability to prevent the occurrence of acid gradients. The negative cross-rib design is like building hundreds of small traversing dams on top to prevent heavy mountains from flowing down.

In addition to preventing acid stratification, the design of negative cross ribs can also help in other areas. In the case of rapid discharge, the rate at which acid diffuses to the cathode is often a limiting factor when high power is required. Therefore, the negative cross-rib design creates hundreds of mini-dams, one after another, of hundreds of mountains that evenly cross the electrode surface. So far, we have covered possible mechanisms to prevent acid stratification and improve power transfer. DuraLife separators were found to improve power transfer and reduced acid stratification in micro-hybrid battery tests. In future tests, we will better understand the various mechanisms and strengthen the separator's contribution to these new applications.

Another example for prolonging the life of a deep cycling battery is to prevent shedding of positive active materials. To this end, the separator is often combined with a non-woven laminate such as a glass mat (see Fig. 27). The laminate structure is generally applied to the surface of the separator in direct contact with the anode. There have been commercial approaches for extending the functional life of deep cycling batteries over the years. However, the previous laminate structure lowered the battery's power output. In micro-hybrid batteries, the application demands to simultaneously improve cycling capability and power output.

Accordingly, studies to optimize the laminate structure for micro-hybrid applications have been conducted until recently. First, the laminate must have mechanical properties that prevent shedding of the active material during the expected life of the battery. To meet these needs, the laminate must be made of a fiber structure and a material that is resistant to oxidative attack. Second, the laminate should release as little acid as possible to maximize the availability of the acid. It implies that it is the lowest basis weight material to release as little acid as possible. As the basis weight decreases, the mechanical properties often deteriorate. Therefore, the goal is to optimize these properties simultaneously. Another goal is to make the laminate at the bonding point of the two materials (separator, laminate) with a low basis weight. A common technique for bonding materials is to apply an adhesive to the separator and the rib surface of the laminate, but in the case of thin laminates the adhesive often wicks into adjacent layers, creating process problems. Another bonding approach is to weld the laminate structure to the top of the ribs at a speed of sound, which removes the adhesive from the entire system. This kind of approach is only practical if the laminate has an effective amount of synthetic fiber in the mat.

Although not inherently clear, there are other laminate criteria that can substantially limit the energy conversion of the battery, i.e. gas entrapment. When a lead acid battery is overcharged, hydrogen and oxygen are formed due to the hydrolysis of water. In open batteries, these gases will eventually escape. However, for a certain period of time, these gases will adhere to the surface of the included laminate structure to extend the life of the electrode, separator and battery. When the gas is trapped, the electrolyte is pushed out into the space between the electrodes, as evidenced by an increase in the height of the electrolyte in the battery. Since the gas is a heavy insulator, the path of ion conduction is greatly reduced. Therefore, optimizing the laminate to minimize gas entrapment plays an important role in maximizing the power and electrical capacity of lead-acid batteries in deep cycle or micro-hybrid applications.

Referring to Figure 28, an overview is disclosed. Over the past 100 years, lead-acid batteries have evolved in the most evolutionary way for the diverse demands of new applications. In order to meet these needs, changes have been made to the material of the structure, including the separator. During this time, separators have been transformed into synthetic materials such as Ultra High Molecular Weight Polyethylene (UHMWPE). In order to prevent shorts, improved oxidation resistance for extended life and prevent side and bottom shorts due to packaging possibilities, these synthetic materials allow the separator to become microporous. This type of PE separator offers the possibility of adding other functions, such as the inclusion of additives into the separator, to prevent antimony toxicity and reduce the associated water loss.

In order to meet new market opportunities such as micro-hybrids, we are convinced that a material change of the structure including the separator is required (see Fig. 29). Micro-hybrid applications require high power to crank the engine as found in traditional SLI batteries and the frequent cycling found in deep discharge batteries. In order to enhance the power, we preferably modified the separator to lower the electrical resistance and increase the available acid by minimizing gas entrapment in the separator. To prolong battery life, we fixed the acid, which prevented acid stratification. Next, we added the laminate to keep the active material in place. This design change focuses on optimizing the three properties of the laminate simultaneously: basis weight, mechanical properties and gas trapping. In order to improve the performance of micro-hybrid open batteries, not only design changes have been made and proposed, but also changes in separators and laminates are effective.

Meeting the challenges for micro-hybrid applications can have advantages in other applications currently maintained by lead-acid batteries. For example, modifications of separators to minimize acid stratification, reduce gas entrapment, maximize acid volume, reduce electrical resistance, and extend life can be delivered directly to current battery applications. These evolutionary changes have made revolutionary separators, and their good price against competing technologies makes lead-acid batteries an excellent choice in the ISS and micro-hybrid markets.

In accordance with embodiments of the present invention, separators with preferably novel, improved, and/or complex performances, such as deep cycle or ISS or micro-hybrid separators, minimize acid stratification in open lead acid batteries, and traditional separators It occupies about 15% less volume compared to, has negative cross ribs, has a large number of small mini-ribs in the horizontal direction, has a mechanical barrier that prevents the occurrence of acid concentration gradients, and is uniformly across the surface of the electrode. It has hundreds of mini dams for mini pools of hundreds of mountains to be formed, improving power transfer and reducing acid stratification in micro batteries, etc.

According to one object of the present invention, battery separators, lead acid battery separators, open lead acid battery separators, reinforced open lead acid battery separators, ISS or micro-hybrid battery separators having improved, unique, high performance, and/or complex performance. , ISS open lead-acid battery separator, ISS reinforced open lead-acid battery separator, a battery comprising such a separator, a system or vehicle including such a battery or separator, a manufacturing method, a method of use, and the like are provided.

31 to 34 relate to a leaf or piece type separator. FIG. 31 is a perspective view of the lead-acid battery broken, which shows the exterior of a leaf or piece such as the Daramic Industrial PE Leaf separator or Daramic Auto PE Leaf separator of FIG. 33. The Daramic Industrial PE Leaf separator of FIG. 33 is shown with an enlarged cross-sectional view of each of the additional glass mat laminates.

According to an embodiment of the present invention, a new or improved battery, separator, component and/or composition having heavy metal removal capability and/or a method of making and/or using the same is provided. According to a preferred embodiment of the present invention, a new or improved lead-acid battery with heavy metal removal ability, single or multi-layer lead-acid battery separator, battery casing, battery part, porous bag, laminate, coating, surface, filler, electrode formulation , Lead-acid battery components such as electrolytes, and/or polymer or resin compositions, and/or methods of making and using them. According to a more preferred embodiment of the present invention, a new or improved lead-acid battery having a heavy metal removal ability and using at least one PIMS mineral as at least one filler component, a lead-acid battery separator of a single or multiple layers, a lead-acid battery component, for example, For example, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrode formulations, electrolytes, etc., and/or polymer or resin compositions. In the microporous lead-acid battery separator according to an embodiment of the present invention, PIMS minerals, preferably fish mill, and bio-mineral are silica-filled lead-acid battery separators, preferably a part of the silica filler component in the polyethylene/silica separator formulation. It is provided to replace. According to an embodiment of the present invention, there is provided a battery separator, a method of manufacturing a battery separator, a method of using the battery separator, an improved battery separator and/or an improved separator or laminate for a lead-acid battery.

According to one embodiment of the present invention, a new or improved battery, separator, component and/or composition and/or method of manufacture and/or use with heavy metal removal capability is provided. According to a preferred embodiment of the present invention, a new or improved lead-acid battery with heavy metal removal ability, single or multi-layer lead-acid battery separator, battery casing, battery part, porous bag, laminate, coating, surface, filler, electrode, electrolyte Lead acid battery components such as and/or polymer or resin compositions and/or methods of making and/or using them are provided. According to a more preferred embodiment of the present invention, at least one raw material of natural and/or synthetic hydroxyapatite having heavy metal removal ability and heavy metal binding ability is used, wherein at least one PIMS mineral is used as at least one filler component. Lead-acid battery components including new or improved lead-acid batteries, single or multi-layer lead-acid battery separators, battery casings, battery parts, porous bags, laminates, coatings, surfaces, fillers, electrodes, electrolytes, and/or polymer or resin compositions. Is provided. In the microporous lead-acid battery separator according to an embodiment of the present invention, PIMS minerals, preferably fish mills, bio-minerals are silica-filled lead-acid battery separators, and preferably replace at least some of the silica filler components of the polyethylene/silica separator formulation. Is provided to

According to an embodiment of the present invention, a new concept of using a Phosphate Induced Metal Stabilization (PIMS) mineral as a filler component in a microporous lead-acid battery separator is provided. According to one embodiment of the present invention, PIMS minerals, preferably fish meal, bio-minerals are provided to replace at least some of the silica filler components in a silica-filled lead acid battery separator, preferably a polyethylene/silica separator formulation. .

As mentioned earlier, a common failure mode in the lead-acid battery industry is a "hydration short" phenomenon. According to one embodiment of the present invention, a new or improved battery, separator, component and/or composition with heavy metal removal ability to deal with, delay, reduce, or eliminate a "hydration short" phenomenon is provided. .

According to one embodiment of the present invention, various PIMS minerals have been identified, some of which have been demonstrated to have lead affinity (see Tables 1 and 2). Fish bones, for example PIMS minerals derived from commercial and experimental ground fish mills, showed very high lead ion affinity compared to other samples. Fish bone or fish mill powder was extracted in a typical lead acid battery separator format through pilot operation at several loading concentrations. This PIMS-containing separator was evaluated to have lead removal performance; It has been demonstrated to significantly reduce lead concentration in acidic solutions. For example, a% Pb reduction of 17% to 100% has been demonstrated. Fish bone powder may be added to replace a portion of the silica filler at a substitution level of 1% to 20%, more preferably 2% to 10%, most preferably 2% to 5% of the silica. According to one embodiment of the present invention, ground fish bone powder, for example ground fish mill, is about 1% to 50% or more, more preferably about 5% to 30%, most preferably 10% to 20% of silica. % Substitution level can be added to replace some of the silica filler.

The bio-minerals of battery separators can be commercially used in extrusion-molded polyolefin polymer resins and porous polymer films or membranes.

According to an embodiment of the present invention, lead reduction can be achieved by including PIMS minerals, preferably PIMS minerals derived from fishbone, in a lead-acid battery separator.

The present invention presents a new chemically active microporous membrane substrate. A wide range of chemically active or reactive mineral fillers are applicable to membrane injection and extraction processes. These minerals are available at low cost at the desired level of purity and, in the case of fishbones, are industrial wastes available from a variety of sources. As well as simplifying the battery manufacturing process containing sodium sulfate, the low cost of raw materials is an advantage.

Preferred separators are, for example, microporous materials having pores of 1 micron or less, but other materials of porosity or macroporousness may also be considered. For example, a macroporous separator having a void greater than 1 micron may include a separator made from rubber, PVC, synthetic wood pulp (SWP), glass fiber, cellulose fiber, polypropylene, and combinations thereof.

According to one embodiment, the battery is a lead calcium battery such as a lead acid battery or vented or flooded lead acid battery, a reinforced open lead acid battery (EFB), a valve regulated lead acid (VRLA) battery, a low-maintenance lead acid recharge. Battery, absorbent glass mat (AGM) battery, VRLA AGM battery, gel battery (gel cell), VRLA gel battery, sealed lead acid battery, recombination battery, polymer battery, carbon lead acid battery or other batteries, capacitors, supercapacitors , Accumulator, battery/capacitor combination, etc. A preferred battery is a vented or flooded lead acid battery.

According to one embodiment, the battery separator is a lead-acid or lead-calcium battery separator such as a flexible or rigid separator, a pocket, an envelope, a sheet, piece or leaf separator, a single or multiple layer separator, a composite or laminate separator, a vented or flooded) lead acid battery, reinforced open lead acid battery (EFB), valve controlled lead acid (VRLA) battery, low-maintenance lead acid rechargeable battery, absorbent glass mat (AGM) battery, VRLA AGM battery, gel battery (gel cell), VRLA gel battery , A sealed lead-acid battery, a recombination battery, a polymer battery, a carbon lead-acid battery or another battery, a capacitor, a supercapacitor, an accumulator, and a separator for a battery/capacitor combination. A preferred battery separator is a vented or flooded lead acid battery separator.

Hydroxyapatite is a mineral with proven heavy metal binding ability. Hydroxyapatite can be synthesized and purified like nanocrystalline materials. Hydroxyapatite is found in the skeletal structures of many plants and animals in nature, as well as in the minor constituents of natural minerals such as kaolinite. The most common animal-derived sources of hydroxyapatite are aquatic, for example fish, crustaceans, shellfish, and land-based animals such as cattle and pigs. The most common plant-derived sources of hydroxyapatite are tea, seaweed, and various types of bark. With all natural products, varying degrees of purity and efficacy can be expected. For example, fish meal is commercially available within a range of purity depending on the level of decomposition of the non-skeletal residue. That is, fish meals can contain large amounts of protein from the remaining fleshy components; This can be called'high-nitrogen' fish meal. Fish wheat, which has been completely degraded by protein, leaves the skeleton intact and can become'high-phosphate' fish wheat.

Hydroxyapatite, derived from most animals and plants, is supplied commercially as a coarse particulate material. According to one embodiment of the present invention, in order to efficiently use a hydroxyapatite-containing material, it is preferable to perform a milling or grinding process of reducing the particle size and increasing the surface area so that hydroxyapatite can be optimally exposed to heavy metals. . The milling process may promote particle introduction into the battery, for example by film injection, impregnation, coating, laminating, molding, bag making or a combination of these techniques. For example, in order to obtain an optimal environment for including the ground fish mill into the battery separator through the twin screw extrusion method, the particle size of D50 is preferably 10 μm to 80 μm. The aforementioned particle size range is also preferred when the natural hydroxyapatite particles are incorporated into the nonwoven laminate-separator structure by impregnation, coating, molding, and bulk powder bag type delivery methods.

According to one embodiment of the present invention, a hydroxyapatite source, for example a ground or ground fish mill, is mixed with a separator injection formulation, for example a polymer/silica/fish mill formulation or a polymer/silica/fish mill/oil formulation. It is preferable to mix. A separator made in this way provides desirable electrochemical performance to known lead-acid battery separators, but surpasses that of conventional separators by active sequestration in solution. In deep discharge conditions, the electrolyte contains reduced lead to a high level, passing through a deep and complex separator matrix, and the separator according to an embodiment of the present invention is an extruded fixed hydroxyapatite, e.g., to extract the lead element before moving to the cathode. For contains fish wheat. Therefore, according to a preferred embodiment of the present invention, the raw material of hydroxyapatite is fixed by incorporating it into the separator injection process using the possibility of surface contact and proximity to the electrode requiring protection.

Other approaches to include hydroxyapatite into the separator and/or battery are adjacent to and/or attached to the separator by means of attachment such as welding, spot welding, ultrasonic welding, bonding, heating, heating and pressing or other known processes. The inclusion of reactive materials as a laminate mat. The laminate may be a glass mat, and fish mill or other raw material of hydroxyapatite may be mixed with a binder during formation of the glass mat, coated on the mat, and/or impregnated into the mat. Fish mill or other raw materials of hydroxyapatite can be extracted with resin during the fiber process to be included in the wet-laid process as well as the carded dry process of the nonwoven fabric. Alternatively, fish mills or other raw materials of hydroxyapatite can be added to the binder in synthetic nonwovens such as PBT, PET, PP, or added directly prior to wet-lay fiber formation. This method is also useful when adding fish meal or other raw materials of hydroxyapatite to a cellulose laminate such as "pasting paper". One or more hydroxyapatite raw materials may be included in the separator using, for example, coating adhesion after formation of the separator, direct inclusion after formation, contacting the separator with inorganic and organic fiber laminate materials, and/or a combination thereof.

Another way to include hydroxyapatite, such as ground fish mill, is to coat the fish mill directly on the positive and/or negative surface of the separator. An example of such a method is to make a slurry in a predetermined concentration and coat the positive or negative surface with a slurry using known coding means, e.g. dip, spray, roller, nip coating, etc., and then continue prior to battery construction and formation. The slurry-separator is dried to fix the fish mill during the ongoing separator process step. Therefore, the raw material of hydroxyapatite can be applied to a vehicle, for example by mixing water or other solvents or binders, to make a mixture or slurry suitable for application to a surface coating, preferably a porous coating.

Another way to incorporate hydroxyapatite in an energy storage device is to mix an active material such as fish meal with a resin used to make container hardware for batteries, such as cases, supports, dividers, covers, etc. Therefore, the electrolyte solution can contact the surface of the resin case, the support, the divider, the top cover, and related parts including the battery configuration for a predetermined time. In addition, the parts comprising the battery construction can be injection molded by a method of including an active material such as fish mill, ie a reactive mineral as the inner surface at a relatively high concentration; This is generally referred to as'in-molding'. In addition, in order to store hydroxyapatite in a free electrolyte solution, the encapsulation device incorporating the bulk powder into a porous, non-woven fabric, paper and/or plastic packaging material or other design may contain an activator, i.e., a reactive mineral, a fish mill impregnated glass fiber, glass mat or Other non-woven packing materials, time release beads, and electrolytes such as gels containing reactive minerals may be useful for dissipating rapidly or over time. Incorporating hydroxyapatite directly into the electrolyte bulk reservoir can be used to provide a fixed amount of material at any time during the battery manufacturing process, or during electrolyte injection just prior to battery formation. It is also possible to mix hydroxyapatite, such as fish meal, into a coating of electrochemically active material applied to the anode and cathode respectively. The process of preparing the active chemical and applying the active material to the electrode grid may be modified to include the addition of fish meal or other hydroxyapatite material. Reactive minerals can be included in electrochemically active electrode formulations. As a result, hydroxyapatite may be useful as an additive to extend the life of the battery. For example, after a predetermined service period, a certain level of hydroxyapatite is injected into the battery, thereby preventing depolarization and “hydration short” of the negative electrode, thereby increasing the lifespan.

According to the examples of the present invention and the test of hydroxyapatite, Table 1 below shows that unexpected results can be obtained even when hydroxyapatite such as fish meal is included in a low content. For example, when the battery separator of Sample G contains 10% fish meal by replacing the silica filler, the surprising result is a reduction of 72.6% lead in a 20 ml Pb solution.

[Table 1]

The silica-filled sample E control separator shows a 19.9% Pb reduction. However, the control membrane data are subject to the reversible absorption and removal mechanism of precipitated silica. When silica is replaced with a hydroxyapatite source (Sample F), the absorption mechanism is gradually hampered and eventually replaced by the PIMS removal binding mechanism (Sample G). That is, the reduction of Pb in samples F and G is permanent bonding or removal, compared to the transient absorption by sample E.

Samples B, C and D neat samples were previously immersed in water and precipitated in the Pb assay solution; It was observed that the solution was in full contact with the powder.

Samples E, F and G separator samples were treated with commercially available surfactants at levels comparable to those used for typical lead acid battery separators.

All membrane samples were pre-soaked in water and precipitated in the Pb assay solution; Full contact with the surface and inner holes was observed.

According to the examples of the present invention and the test of hydroxyapatite, Table 2 below shows that surprising results can be obtained even if the hydroxyapatite such as fish meal is included in a low content. For example, if the battery separator of Sample L contained 10% fish meal by replacing the silica filler, the unexpected result was that lead was reduced to 56.2% in a 20 ml Pb solution. In addition, when the battery separator of Sample M contained 50% fish meal by replacing the silica filler, lead was reduced to 99.6% in a 20 ml Pb solution, showing a surprising result of virtually complete removal.

[Table 2]

Samples E and I control separators (silica-filled-70%) show Pb reductions of 15.4% and 23.9%, respectively. However, the control membrane data are subject to the reversible absorption and removal mechanism of precipitated silica. When silica is replaced with a hydroxyapatite source (samples J and K) such as fish meal, the absorption mechanism is gradually hampered and eventually replaced by the PIMS removal binding mechanism (samples L and M). That is, the reduction of Pb in samples L and M is permanent binding or removal, compared to the transient absorption by samples E and I.

Samples B, C, D and N neat samples were previously immersed in water and precipitated in the Pb assay solution; It was observed that the solution was in full contact with the powder.

Samples E to M separator samples were treated with commercially available surfactants at levels comparable to those used for typical lead acid battery separators.

All membrane samples were pre-soaked in water and precipitated in the Pb assay solution; Full contact with the surface and inner holes was observed.

The Pb assay test method was carried out through ICP/MS EPA Method 200.8. All samples were soaked statically without stirring for 48-72 hours. Phosphoric acid levels of all samples Post Exposure were tested and found to be below the maximum acceptable level.

Inorganic or mineral compound groups are known to effectively bind heavy metals such as lead, cadmium, iron, zinc and copper. The mechanism by which minerals bind heavy metals is referred to as PIMS (Phosphate Induced Metal Stabilization), and is widely used for environmental restoration of heavy metals from contaminated soil and water. In environmental restoration applications, large amounts of minerals that treat PIMS affinity for toxic metals may be mixed with contaminated soil or contaminated water to reduce heavy metal contamination may be contained within a housing that passes through a bulk PIMS mineral cake.

According to an improved environmental improvement embodiment of the present invention, we use hydroxyapatite (HA) or hydroxyapatite, for example synthetic and/or natural hydroxyapatite, preferably PIMS mineral, more preferably ground fish bone or wheat. At least one raw material is a polymer structure with a high surface area, preferably a porous polymer membrane, more preferably a microporous polyolefin membrane such as a flat sheet or hollow fiber, most preferably a filler, preferably a silica-filled microporous polyethylene. A new concept of adding PIMS minerals to microporous polyethylene membranes using PIMS minerals as a partially substituted filler for the silica-filled components of the membrane is proposed. The hydroxyapatite mineral filled membrane can be used as a filler medium, packing, liner, etc., and can remove heavy metals from contaminated liquids such as water.

According to an embodiment of the present invention, new or improved batteries, separators, components and/or compositions are one or more chemically active or reactive, natural or synthetic, mineral fillers, particles, coatings, adjuvants, etc., preferably from bone or teeth. It has the ability to remove heavy metals through the chemically active properties provided by bio-minerals, more preferably fishbones or wheat. These new or improved batteries, separators, components and/or compositions have advantages such as low cost of raw materials, lead removal, reduced demand for sodium sulfate, increased battery coverage, recycling or the use of industrial wastes or by-products.

According to one embodiment of the present invention, we:

In order to combine Pb in the solution and reduce the occurrence of hydration short during the life of the battery, the current process of manufacturing the separator in the battery separator and a gelatinizable material are included,

We included materials from common and reusable sources:

-Fish: Most efficient at low or very low pH

* Bone

*scale

-Crustaceans: Functional range similar to fish wheat

* Exoskeleton

-Shellfish: Most efficient in general environments above pH 8.5

* skin

-Beef: functional range similar to fish wheat

* Bone

-Pit: functional range near neutral pH

* Humus, decayed plant material

-Tea by-product: functional range near neutral pH

* By-products of the tea making process, stems and undesirable leaves

The preferred fish wheat was defined as the “top image” fish species.

*- Small, prickly fish that is not edible

-Shellfish can also constitute minor components.

-Fish meal is essentially bones and scales after purification, cleaning, drying and grinding.

* Typically between 4 and 6% residual oil remains in the fish mill.

* Fish meal is composed of mineral apatite w/formula:

* Ca _10-X Na _X (PO ₄ ) _6-X (CO ₃ ) _X (OH) ₂

According to a preferred embodiment of the present invention, a battery separator including one or more PIMS minerals as a filler component, a battery separator including a fish bone or fish mill filler, and a silica including fish bone powder to replace at least a portion of the silicon filler Battery separators, and/or methods of making or using them are provided.

Lead-acid batteries, for example open-type lead-acid SLI batteries, include a negative electrode plate (electrode) and a positive electrode plate (electrode) with a separator interposed therebetween. These components are housed in a container that also includes terminal posts, vents and gang-vent plugs. According to a preferred embodiment, the separator has transverse ribs on a surface facing the cathode and includes longitudinal ribs on the surface facing the anode (see, for example, FIGS. 5 and 26). Although a specific battery is shown in FIG. 31, the creative separator includes, but is not limited to, shielded lead acid, open lead acid, ISS lead acid, combined battery and capacitor units, other battery types, capacitors, accumulators, etc. It can be used for various types of batteries or devices.

The preferred separators of FIGS. 5 and 26 are porous polymer membranes such as microporous polyethylene membranes having pores of about 1 micron or less. Nevertheless, creative separators are microporous or made of natural or synthetic materials such as polyolefin, polyethylene, polypropylene, phenolic resin, PVC, rubber, synthetic wood pulp (SWP), glass fiber, cellulose fiber, or combinations thereof. It may be a macroporous membrane having pores larger than a micron, more preferably a microporous membrane made from a thermoplastic polymer. Preferred microporous membranes have a pore radius of about 0.1 microns, ie 100 nanometers, and may have a porosity of about 60%. In principle, the thermoplastic polymer can contain any acid resistant thermoplastic material suitable for use in lead acid batteries. Preferred thermoplastic polymers include polyvinyl and polyolefin. Polyvinyl includes, for example, polyvinyl chloride (PVC). Polyolefins include, for example, polyethylene, ultrahigh molecular weight polyethylene (UHMWPE) and polypropylene. Preferred embodiments may include a mixture of fillers such as silica and/or reactive materials and UHMWPE. In general, a preferred separator precursor can be made by mixing about 30% by weight filler, about 10% UHMWPE and about 60% by weight processing oil in an injection machine. The mixture also contains a small amount of additives or adjuvants commonly used in the art, such as wetting agents, pigments, charging additives, and the like, and can be injected into the shape of a flat sheet. The rib is preferably formed by the engraved surface of the opposite calender roller. After that, a lot of processing oil is extracted and a microporous membrane is formed.

5 and 26, according to one embodiment, when the total thickness of the separator is about 30 mil, the negative cross rib is about 4 mil thick, the back web is about 6 mil thick, and the positive rib is about 20 mil thick. Preferred separators are wraps, envelopes, pouches, pockets or synthetic nonwovens with or without cut piece or leaf separators (Figure 33) or additional laminates (Figure 27), and minor cross-sections opposite the separators with major longitudinal ribs. It may include cross ribs.

A transverse cross rib formed on the opposite side of a separator with longitudinal ribs is required for high speed fabrication and assembly, including reduction of backweb mass, reduced ER, reduced cost and high speed separators, envelopes, and/or battery production and/or assembly. Protects the sheet and increases its stiffness by allowing an increase in physical properties that can be used. These separators or precursors may be produced in rolls, envelopes or pockets and pieces, and may be used when producing separators by high-speed automation or manually, and high productivity is expected.

In addition, by adding a major vertical rib opposite to the transverse or cross rib, for example, it is possible to reduce the mass of the separator while maintaining the internal performance and physical properties required for the process. If a cross rib is added on the opposite side to achieve the desired overall separator thickness for the major rib + back web + cross rib, the mass of the major rib can be reduced. By adding transverse or cross ribs, it is possible to reduce the thickness and/or mass of the sheet while maintaining productive properties such as stiffness and protecting the sheet from wear and oxidation rips and tears over the life of the battery. have.

According to an embodiment of the present invention, small, tight transverse ribs are added to one side of the lead acid separator in contact with the cathode, preferably a major rib is added to the anode. The small, tight negative transverse ribs can be of many different shapes, without limitation, can have a sinusoidal curve, diagonal or straight rib pattern, and can be continuous or discontinuous. For the convenience of the process, a round-shaped straight rib may be preferred.

The positive vertical major ribs may have many shapes in an almost vertical direction, for example a sinusoidal curve, a diagonal, a continuous or discontinuous straight rib. For the convenience of the process, a round-shaped straight rib may be preferred. Certain battery designs, often referred to as Japanese designs, lack positive ribs and are instead replaced by heavy glass mats laminated to the flat positive face of the separator. In this glass matte positive face separator embodiment, the transverse negative rib of the present invention performs the same type of function as in the embodiment with positive vertical ribs. The positive face can be smooth or flat, has protrusions, has ribs, or can have a nonwoven fabric bonded or laminated thereto. These non-woven materials may be formed from synthetic, natural, organic or inorganic materials or blends such as fiberglass, polyester (PET), recycled PET or combinations thereof with or without unique reactive materials. The separator may be a cut piece separator, or a separator in the form of a wrap, envelope, pouch, or pocket.

The separator according to an embodiment of the present invention includes:

1) Transverse rib height-preferably about 0.02 to 0.30 mm, most preferably about 0.075 to 0.15 mm.

2) sheet, ie substrate thickness-preferably 0.065 to 0.75 mm.

3) The total thickness of the positive rib + back web + negative rib-the total thickness of the separator is preferably about 0.200 to 4.0 mm.

4) Mass reduction-preferably greater than 5%, more preferably greater than 10%. The transverse ribs increase the transverse strength of the separator and reduce the backweb or substrate thickness. Mass can be removed from the backweb and positive rib while maintaining and increasing the transverse strength. In addition, the transverse negative rib also contributes to the overall thickness of the separator. Therefore, the height of the vertical positive rib can be directly reduced by the negative cross rib.

5) Separator type-The separator is a porous material, for example a microporous or macroporous thermoplastic material, preferably polyethylene, polypropylene, polyvinyl chloride and mixtures thereof, as well as rubber, polyolefin, phenolic, crosslinked phenol. It can be made of resin, cellulose, glass, or a combination thereof.

Other benefits of adding negative cross ribs include:

1) Reduced electrical resistance-The negative cross rib profile design allows the mass to be reduced while maintaining the same or higher transverse bending stiffness, so the observed electrical resistance will be lower.

2) Minimize tear propagation-When the separator is severely oxidized, cracks or splits occur in the back web and are likely to extend parallel to the major vertical ribs. Negative cross ribs will prevent tear propagation due to the extra mass of the ribs, for example.

In the side alignment-assembly process, the wrapped plate 1) The plate is arranged horizontally and vertically before the string is connected to the positive and negative electrodes respectively. For vertical arrangements, positive ribs provide a means to allow the separator and plate to slide when they are in contact with each other. For a typical arrangement, the negative plate can slide when in contact with the flat backweb. Negative transverse ribs will provide less surface area and aid in the alignment process.

According to an embodiment of the present invention, the separator is composed of ultra-high molecular weight polyethylene (UHMWPE) mixed with processing oil and a filler of precipitated silica and/or reactive minerals. According to an embodiment of the invention, the negative cross ribs preferably have a 2-6 mil radius and a 10-50 mil rib space.

According to an embodiment of the present invention, the battery separator includes a porous membrane having a back web, at least two rows of positive ribs formed on the positive side of the back web, and a plurality of negative cross ribs or transverse ribs formed on the negative side of the back web. The positive rib may have a straight or wave shape, may have a solid region, and may have a pyramid shape with a cut end. The membrane may be selected from the group consisting of polyolefin, rubber, polyvinyl chloride, phenol, cellulose, or a combination thereof, and the membrane is a polyolefin material forming a battery separator for a storage battery.

The battery separator is used to separate the positive and negative electrodes of a battery, and is generally microporous, so that ions can pass through the positive and negative electrodes. In lead/acid storage batteries, in the case of automotive or industrial batteries, the battery separator is a microporous polyethylene separator having a backweb and a plurality of positive ribs on the backweb. Separators for automobile batteries are generally made of continuous length, rolled, continuously folded, and sealed along the edges to form a pouch containing electrodes for the battery. The separator for industrial traction batteries is a piece separator that is cut to approximately the same size as the electrode plate.

In a method of making a lead/acid battery separator from a sheet of plastic material according to an embodiment of the present invention, the sheet is calender molded to form cross or negative side transverse ribs or protrusions, preferably positive vertical ribs and opposite sides of the sheet. It is calendered to form negative crossing or transverse ribs at the same time.

When the battery is sufficiently charged and current is continuously applied, i.e., overcharged, hydrogen is produced at the cathode and oxygen is produced at the anode. Since hydrogen is formed at the cathode, this may cause the separator to be moved away from the cathode, thereby forming a gas pocket that prevents the discharge of gas. An embodiment of the present invention addresses this issue and provides an improved battery separator. For example, negative cross ribs formed on the back or on the negative surface can be blocked by flats, fissures or recesses behind each positive rib (see FIG. 26). Flats, fischers or recesses can form vertically extending channels, can discharge hydrogen gas, and can extract plasticizers or lubricants from positive ribs. A separation membrane having a channel through which hydrogen gas can be discharged may be desirable.

In one embodiment, the separator is made of a microporous, thermoplastic material, which includes a vertical positive rib and a horizontal negative rib, wherein the vertical rib is generally higher than the horizontal rib, and the vertical and horizontal ribs are formed from plastic. It is a solid rib, and the transverse rib extends over the entire back width of the separator. The separator sheet thickness is about 0.10 to 0.50 mm, the height of the vertical rib is 0.3 to 2.0 mm, the height of the horizontal rib is 0.1 to 0.7 mm, the vertical stiffness with a width of 100 mm is about 5 mJ, and the horizontal stiffness is about 2.5 mJ, The total thickness of the separator is 2.5mm or less.

The separator according to the embodiment of the present invention is a pattern similar to a conventional polyethylene separator having a negative roll having a groove for forming a negative cross rib, a negative roll having no groove or a low depth groove, and the addition or substitution of a reactive mineral filler. It can be manufactured as Preferably, the plastic material comprising the filler is injected through a slot die for forming a film, and passed through two calender rolls, i.e. a positive roll, a negative roll, by means of which a positive longitudinal rib and a negative transverse rib are made, The separator sheet can be reduced to a desired thickness. The positive roll may include shallow circumferential or annular grooves forming positive vertical ribs, and lands or smooth regions or stripes forming smooth regions of the separator to seal the edges of the pockets. The negative roll can have shallow axial grooves forming cross ribs. In addition, the negative roll may have gaps formed between smooth lands or regions, for example shallow axial grooves with welded regions.

The separator according to the embodiment of the present invention having negative cross ribs may have better mechanical workability compared to the case without transverse ribs, and may have better membrane guidance due to the result of improved transverse stiffness, and improved transverse stiffness. Due to the stiffness, the processability for positioning the electrode in the pocket can also be improved. In addition, a separator having a reduced sheet thickness and consequently reduced electrical resistance must be produced to increase battery output with a constant battery volume. The separator according to the present invention should be able to be carried out to form pockets without difficulties for conventional machines. The additional transverse negative ribs should not cause problems in performing mechanical processes to create pockets or weld pockets using thermal or ultrasonic means.

According to an embodiment of the present invention, a separator made of elastic plastic suitable for use in a lead-acid storage battery includes an inner region and a sheet material including two peripheral regions, and the longitudinal direction in the inner region spaced more widely than the peripheral region. It includes a positive rib formed with vertical ribs and a negative rib formed in a horizontal direction.

The new or improved lead-acid battery preferably comprises a housing comprising an anode away from the cathode, a porous separator positioned between the anode and the cathode, an electrolyte for ion exchange between the anode and cathode, and includes a housing, a separator, an anode, a cathode. And at least one of the electrolytes comprises at least one natural or synthetic hydroxyapatite mineral.

The new or improved lead-acid battery preferably comprises a housing comprising an anode away from the cathode, a porous separator positioned between the anode and the cathode, an electrolyte for ion exchange between the anode and cathode, and includes a housing, a separator, an anode, a cathode. And at least two of the electrolytes contain at least one natural or synthetic hydroxyapatite mineral.

The new or improved lead-acid battery preferably comprises a housing comprising an anode away from the cathode, a porous separator positioned between the anode and the cathode, an electrolyte for ion exchange between the anode and cathode, and includes a housing, a separator, an anode, a cathode. And at least three of the electrolytes contain at least one natural or synthetic hydroxyapatite mineral.

The new or improved lead-acid battery preferably comprises a housing comprising an anode away from the cathode, a porous separator positioned between the anode and the cathode, an electrolyte for ion exchange between the anode and cathode, and includes a housing, a separator, an anode, a cathode. And at least four of the electrolytes contain at least one natural or synthetic hydroxyapatite mineral.

The new or improved lead-acid battery preferably comprises a housing comprising an anode away from the cathode, a porous separator positioned between the anode and the cathode, an electrolyte for ion exchange between the anode and cathode, and includes a housing, a separator, an anode, a cathode. And each of the electrolytes comprises at least one natural or synthetic hydroxyapatite mineral.

The new or improved separators of the present invention include starting, deep-cycling and stand-by power battery applications, such as lead-acid battery separators, or open, gel and AGM battery types, i.e. start, stop, motive power and deep cycle lead-acid battery applications, as well as open-type And use for specific lead acid battery applications and/or premium lead acid gel batteries. In addition, these separators can be applied to other batteries, accumulators, capacitors, and the like.

According to an embodiment of the present invention, at least one hydroxyapatite mineral source, e.g., ground fish mill, is about 1% to 50% of silica, preferably about 5, to replace some of the silica filler in the silica-filled separator. It is preferred to add a substitution ratio of% to 30%, more preferably about 10% to 20%.

According to an embodiment of the present invention, at least one hydroxyapatite mineral source, e.g., ground fish mill, is used as a filler in a packed separator with about 1% to 75% filler, preferably about 5% to 50% filler, more preferably Preferably it is added in a filler ratio of about 10% to 30% filler.

According to an embodiment of the present invention, at least one hydroxyapatite mineral source, e.g., ground fish mill, is used as a filler in the battery separator to about 1 wt% to 75 wt%, preferably about 2 wt% to 35 wt%, more preferably Preferably, it is added in a proportion of about 5 wt% to 20 wt%.

According to an embodiment of the present invention, a new concept of using a PIMS mineral as a filler component in a microporous lead-acid battery separator is provided. According to an embodiment of the present invention, PIMS minerals, preferably fish meal, bio-minerals are provided to partially replace the silica filler component in a silica filled lead acid battery separator, preferably a polyethylene/silica separator formulation.

*According to an embodiment of the present invention, a new concept of using one or more natural or synthetic PIMS minerals as filler components in a microporous lead acid battery separator is provided. According to an embodiment of the present invention, PIMS minerals, preferably fish meal, bio-minerals are provided to partially replace the silica filler component in a silica filled lead acid battery separator, preferably a polyethylene/silica separator formulation. According to an embodiment of the present invention, the present invention deals with new or improved batteries, separators, components and/or compositions and/or methods of manufacture and/or use with heavy metal removal capability.

According to an embodiment of the present invention, a new concept of using PIMS mineral as a filler component in a microporous PE ISS lead-acid battery separator is provided. According to an embodiment of the present invention, PIMS minerals, preferably fish meal, bio-minerals are provided to partially replace the silica filler component in a silica filled lead acid battery separator, preferably a polyethylene/silica separator formulation.

A common type of failure in the lead-acid battery industry is a “hydration short” phenomenon. The traditional approach to avoiding hydration shorts is to add sodium sulfate (Na ₂ SO ₄ ) as an electrolyte solution during battery production. This approach requires additional manufacturing processes and increases the complexity of battery production. The addition of sodium sulfate acts to “block” the hydration short.

According to one embodiment of the present invention, various PIMS minerals have been identified, some of which have been proven to have lead affinity. PIMS minerals derived from fishbone, such as commercial and experimental ground fish meal, showed very high lead ion affinity compared to other natural or synthetic samples.

According to an embodiment of the present invention, lead reduction is achieved by including PIMS minerals in the ISS lead-acid battery separator, preferably PIMS minerals derived from fishbones.

According to an embodiment of the present invention, a new concept of using a PIMS mineral as a filler component in a maceporous ISS lead-acid battery separator is provided. According to an embodiment of the present invention, PIMS minerals, preferably fish meal, bio-minerals are provided to partially replace the silica filler component in a silica filled lead acid battery separator, preferably a polyethylene/silica separator formulation.

According to an embodiment or object of the present invention:

An ISS vehicle battery separator is provided comprising at least one negative cross rib, a silica to polymer ratio greater than 3:1 and at least one PIMS mineral as a filler member.

The ISS vehicle battery separator includes one or more fish bone or fish meal fillers.

The ISS vehicle battery separator is a silica-filled polyethylene battery separator including a fishbone or fishmill filler replaced with at least a portion of the silica filler.

The flooded lead acid battery includes the battery separator for the ISS vehicle.

The ISS electronic system includes the battery.

ISS automotive battery separators feature multiple separators with charge acceptance, power delivery, reduced hydration shorts, improved lifetime and optimized reduced acid stradification at the same time. Includes.

The ISS lead-acid battery includes the separator.

The ISS vehicle includes the battery.

The battery separator has the following improvements, features, changes, transformations, enhancements, performance, characteristics, profiles, shapes, shapes, structures, parts, properties, spaces, and thicknesses. Includes at least three of the ratios, blends, mixtures, formulations, additives, adjuvants, coatings, layers, laminates, mats, nonwovens, surfaces, inclusions, effects, aspects or examples:

1) Charge acceptance/power delivery-Features of separators to help improve charge reception/power delivery, or variations thereof:

a. Low or lower electrical resistance (ER)-Minimization of membrane ER through the following method:

I) lower back-web (BW) thickness-lower the BW thickness from the typical 150-250 microns to 75-150 microns and use negative cross ribs to enhance transversal stiffness,

Ii) increasing the silica to polymer ratio-increasing the content of silica to the polymer content so that the silica to polymer ratio is from 3.0/1.0 to 5.0/1.0,

Iii) Use of silica with high oil absorption and high surface area to increase porosity-typically high surface area (e.g., >200 g/m2) silica with high oil absorption and about 70 to 80% by weight of pore former in the extrusion process. include,

b. Minimize gas entrapment-reduce gas entrapment opportunities:

I) a laminate structure and a modified laminate structure to reduce the strain-gas entrapment,

1. Treat the laminate with chemicals or plasma to modify the surface energy that shedding gas bubbles.

2. Perforated for areas where bubbles will agglomerate and escape the laminate matrix

3. Add nucleating agent

4. Change the structure of the laminate during formation

5. Addition of polymer fibers and/or shaped polymer fibers to the laminate structure

6. Addition of wetting agents or surfactants

7. Reorient the laminate to the fiber structure so that the gas bubbles stick less to the structure.

8. By minimizing the thickness of the structure, the space for bubble attachment is reduced.

Ii. Wetting agent selection-using more hydrophobic wetting agents, using ethoxylated fatty alcohols,

Iii. Negative and/or positive separator cross ribs-with small negative cross ribs to aid in nucleation or transfer of gas bubbles or to allow gas to escape from between the plates or to reduce the likelihood of gas entrapment,

Iv. Nucleation of gas-Has an area acting as a nucleation site on the separation membrane so that gas bubbles emerge from the separation membrane and grow quickly and efficiently to the point where they move between the plates.

1. Profile shape (roughness)-nanostructures are added to the surface of the separation membrane to increase gas nucleation, and the nanostructures can be pyramidal, V-shaped or cylindrical, and can be calendered, laser ablation or controlled. Can be formed by chemical oxidation

2. Additive-An additive is inserted into or onto the matrix of the separator by providing an area on the surface that changes the surface structure or energy to induce nucleation of small gas bubbles formed in a critical volume, and the additive is carbon fiber, May be carbon nanotubes or barium sulfate

2) Prevention, delay, reduction, elimination of hydration short-Add sodium sulfate to the electrolyte to prevent hydration short, or

a. Common ionic effect-including sodium sulfate (e.g., impregnation method) in the separator matrix and/or in the laminate material,

b. Removal of heavy metals-To prevent formation of a hydration short, including apatite, hydroxyapatite mineral, ground fish mill, zeolite, lignin, latex or rubber derivatives in the solution into or on the surface of the separator, laminate materials, electrolytes, battery covers Remove lead ions by

c. Position of the additive-the matrix of the separator, the additive coated on the separator, coated on or in the laminate structure, coated on the container of the battery case before and after the injection molding process, or located in the porous bag or bag of the electrolyte or laminate structure, preferably Has an alternative filler for some of the silica

d. Decreased or reduced acid release-membrane modifications include:

I. A thin backweb-added cross rib, preferably a negative cross rib as discussed above, a lowered backweb (BW) thickness with a high porosity or low rib mass of the separator,

Ii. Serrated/Walled Rib-Use a serrated or walled rib design to reduce the mass of the rib,

3) Improve the service life-transform the separator as follows:

a. Laminate structure-using a laminate to hold a positive active mass in a positive grid

I. Glass mat-using glass mats having different fiber lengths and widths for the mat in the compressed thickness area of 0.1mm to 1.0mm,

Ii. Synthetic non-woven fabric-using non-woven polymer mat, polyester mat,

Iii. Hybrid mat of glass fiber mixed with hybrid-polymer fiber is used,

b. Profile Selection-Contributing to lower mountain deviation by selecting the profile design, using a profile with a shorter rib height, a narrower rib, or a tight rib away from the rampart rib,

c. Polyaspartic acid-Polyaspartic acid is added directly to the matrix of the separator, coated on the separator, coated or added on the laminate structure, coated on the container of the battery case before or after injection molding revolution, or coated on the container of the battery case, or of an electrolyte or laminate structure. Placed in a porous bag or pocket

d. Compressable, flexible and elastic rib structure like I-beam rib profile enhances life

4) acid stratification-overcharge the battery to accelerate the electrolysis of water by several steps,

a. Profile selection-including horizontal ribs across the surface of the separator,

b. Laminate structure-A laminate structure attached to a polyethylene separator is added, fibers are arranged in a predetermined pattern through the material, and a laminate structure is added with the positive and negative faces of the polyethylene separator,

c. Surface Area-Increase the surface area of the separator structure, reduce the fiber diameter of the laminate structure, add the concentration or type of silica, porosity, and increase the inner surface of the separator by cross ribs.

d. Acid immobilization-including cross ribs to place the acid in place, adding a layer of silica on the surface of the laminate and/or separator, adding silica to the laminate to gel the acid, or removing the acid using Daramic AJS technology. Immobilization,

e. Polyethylene/absorbent glass mat hybrid- AGM membrane contains a flat PE membrane as one or inside,

f. Different laminate systems are used, including non-woven fabrics or other glass mats connected with flat PE separators to create hybrid-acceptable separators.

The separator includes negative cross ribs.

The lead-acid battery includes the separator.

Battery separators, such as deep cycle, ISS or micro hybrid separators, comprise at least two of the following:

Helps minimize acid stratification, has about 15% less volume than traditional separators, has negative cross ribs, has a plurality of small mini ribs in the horizontal direction, has a mechanical barrier that interferes with the acid concentration gradient, and has a heavy acid. It has hundreds of mini-dams to flow down, and hundreds of mini-dams that create mini-pools of hundreds of mountains evenly through the surface of the electrode, improving the power transfer of micro-hybrid batteries and reducing acid stratification.

The method of manufacturing a silica rechargeable battery separator includes replacing at least a portion of the silica filler with at least one PIMS mineral.

The lead-acid battery separator includes at least one of a separator, component, or composition having the ability to remove heavy metals using at least one PIMS mineral:

Battery cover, battery part, porous bag, laminate, non-woven fabric, mat, paper, coating, surface, in-mold, filler, electrode, electrode formulation, electrolyte, polymer composition using at least one PIMS mineral and having the ability to remove heavy metals Or a resin composition;

A polymer or resin composition having the ability to remove heavy metals using at least one PIMS mineral as a filling member;

A silica-filled microporous lead-acid battery separator having at least one PIMS mineral replacing at least a portion of the silica filler;

Silica-filled microporous polyethylene lead-acid battery separator having a ground fish mill replacing at least a portion of the silica filler; Or a combination of them.

The present invention may include other forms that do not modify the technical spirit and essential attributes, and accordingly, the detailed description does not indicate the scope of the invention, but is for reference only to the appended claims.

Claims (20)

An array of alternating positive electrodes and negative electrodes; And
Including; a separator disposed between each of the positive and negative electrodes in the array,
The separator includes a porous membrane made of a mixture of a polymer and a filler,
The weight ratio of filler to polymer is in the range of 5:1 or less,
The filler comprises silica,
The membrane has vertical ribs on one side and negative cross ribs on the other side. The method of claim 1,
The polymer is a lead-acid battery comprising one of the group consisting of polyolefin, polyethylene, polypropylene, ultra high molecular weight polyethylene (UHMWPE), phenolic resin, polyvinyl chloride (PVC), rubber, and combinations thereof. The method of claim 1,
The separator is a lead-acid battery further comprising a rubber selected from the group consisting of latex, rubber derivatives, and combinations thereof. The method of claim 3,
The rubber is coated on at least a portion of the surface of the porous membrane lead-acid battery. The method of claim 3,
The rubber is impregnated with at least a portion of the porous membrane. The method of claim 3,
The rubber is mixed with the polymer, and a lead-acid battery used to form a porous membrane. The method of claim 1,
The separator is a lead-acid battery containing a surfactant. The method of claim 1,
The battery is a lead-acid battery operating in at least one of a group consisting of a partial state of charge, an operation, a stop, a backup power application, a cycling application, and a combination thereof. The method of claim 1,
The filler is a lead-acid battery that is a mixture of silica and a Phosphate Induced Metal Stabilization (PIMS) material. The method of claim 9,
The PIMS material is a lead-acid battery containing apatite. In the battery separator for idle stop/start (ISS) vehicle batteries,
It includes a porous membrane made of a mixture of a polymer and a filler,
The ratio of filler to polymer is in the range of 5:1 or less,
The filler comprises silica,
The membrane has vertical ribs on one side and negative cross ribs on the other side,
The vertical ribs are serrated ribs or battlement ribs. The method of claim 11,
The vertical ribs are serrated ribs, and the negative cross ribs are spaced apart more tightly than the vertical serrated ribs. An open lead-acid battery comprising the ISS battery separator of claim 11 or 12. ISS electrical system comprising the open lead-acid battery of claim 13. In the battery separator for idle stop/start (ISS) vehicle batteries,
It includes a porous membrane made of a mixture of a polymer and a filler,
The ratio of filler to polymer is in the range of 5:1 or less,
The filler comprises silica,
The membrane is a battery separator having vertical ribs on one side and mini ribs on the other side. In the battery separator for idle stop/start (ISS) vehicle batteries,
It includes a porous membrane made of a mixture of a polymer and a filler,
The ratio of filler to polymer is in the range of 5:1 or less,
The filler comprises silica,
The membrane has vertical ribs on one side, and the vertical ribs are serrated ribs or battlement ribs. In the battery separator for idle stop/start (ISS) vehicle batteries,
It includes a microporous membrane composed of a polymer and silica,
The weight ratio of silica to polymer is in the range of 5:1 or less,
The membrane has at least one cross rib on one side, the cross rib is perpendicular to a rib on the other side, and the cross rib faces a negative electrode. The method according to any one of claims 15 to 17,
The polymer is a polyolefin separator. An open lead-acid battery comprising the separator of claim 18 with or without a glass mat. A vehicle comprising the open lead-acid battery of claim 19.

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