Title of Invention	IMPROVED CATALYST DESIGN FOR VRLA BATTERIES
Abstract	ABSTRACT Improved Catalyst Design for VRLA Batteries A catalyst device (10) for use with battery cells to recombine oxygen and hydrogen gas and thereby improve the performance and life of such cells. The catalyst device (10) can filter out catalyst poisons and control the temperature of the recombination reactions. A container (14) houses the catalyst (26) within a chamber (22). A catalyst poison filter (28) is provided in the chamber (22) with the catalyst (26). The movement of gas and vapour to and from the chamber (22) is controlled by a micro-porous section (30). The pore size is chosen to allow gas and vapour to pass, but not liquids, and to also prevent a flame from passing ttinough. Pr^a-ably, the micro-porous section (30) Is formed as a disc that seals an opening (20) in the chamber (22). The filter material (28) is then placed as a layer between the catalyst (26) and the opening (20) such that the poison in the gas must pass through the filter material (28) before reaching the catalyst (26). (Fig. 1)

Title of Invention

IMPROVED CATALYST DESIGN FOR VRLA BATTERIES

Abstract

ABSTRACT Improved Catalyst Design for VRLA Batteries A catalyst device (10) for use with battery cells to recombine oxygen and hydrogen gas and thereby improve the performance and life of such cells. The catalyst device (10) can filter out catalyst poisons and control the temperature of the recombination reactions. A container (14) houses the catalyst (26) within a chamber (22). A catalyst poison filter (28) is provided in the chamber (22) with the catalyst (26). The movement of gas and vapour to and from the chamber (22) is controlled by a micro-porous section (30). The pore size is chosen to allow gas and vapour to pass, but not liquids, and to also prevent a flame from passing ttinough. Pr^a-ably, the micro-porous section (30) Is formed as a disc that seals an opening (20) in the chamber (22). The filter material (28) is then placed as a layer between the catalyst (26) and the opening (20) such that the poison in the gas must pass through the filter material (28) before reaching the catalyst (26). (Fig. 1)

Full Text	This application claims the benefit of U.S. Provisional Applications Numbers 60/112,305 filed December 14, 1998, 50/113,579 filed December 24,1998, and 50/148,536 filed August 12,1999, all of which are hereby incorporated by reference. BACKGROUND 1. Field of the Invention The present invention relates to the use of catalysts for improving the service life of valve regulated lead acid (VRLA) cells, and to a catalyst device which may also be applicable to other types of batteries where it is desirable to recombine excess oxygen with hydrogen produced in the battery cell. More particularly, the present invention relates to improved catalyst devices that minimize catalyst poisoning and control the temperature of the catalytic reaction. 2. Background of the Invention Significant improvements to VRLA battery cells can be made with the addition of a catalyst for recombining oxygen and hydrogen gasses within the cells as disclosed in U.S. Application Number 09/022,336 filed 2/11/98, and virtiich is hereby incorporated by reference. One preferred method of adding catalyst to VRLA cells is to couple the catalyst with the pressure relief vent, i.e., the "valve", which provides a convenient means of retrofitting existing cells as well adding catalyst to new cells. A novel catalyst device for use with pressure relief vents is disclosed in U.S. Application Number 09/022,336. While the addition of catalyst provides significant improvement in the performance and of life of VRLA^cells, additional improvements to the catalyst itself, particularly with the structures and devices that support or house the catalyst, are believed necessary to gain the full benefits of the catalyst. High rates of gassing in VRLA battery cells can be caused by conditions such as thermal runaway, malfunctioning power rectifiers, boost charging, charging at abnormally high rates of voltage, and other reasons known in the art. In lead-acid battery cells, oxygen and hydrogen gas is generated due to the electrolysis of water. If a catalyst was installed in a cell experiencing a high rate of gas production, the catalyst would catalyze the oxygen arKi hydrogen to water in a highly exothermic reaction. The resulting enthalpy could generate enough heat to melt many commonly used plastic materials that compose the battery cover, jar or vent cap assemblies. This high reaction temperature can also limit the materials that can be used to house the active catalytic material. One catalyst device as described in the above referenced U.S. Patent Application Number 09/022,336, uses a porous ceramic cartridge to house the catalytic active material. This porous cartridge allows gas to enter the diamber and water vapor to exit the chamber, and prevents the passing of a flame from inside the chamber to outside the chamber if developed due to ignition of the gas^. The temperature achieved, as a result of the exothermic reaction, is governed mainly by the amount of gas produced by the battery. In the normal functioning of a VRLA battery, tiie temperature of reaction is generally not more than 5 to 10F above ambient temp»Bture. However, in the case of high rates of gassing, a higher than normal temperature could occur which could lead to melting of the plastic that supports the catalyst cartridge, that composes the vent cap or that composes the cell jar or cell cover. The high tanpeature could also defonm the pressure relief valve that is pr^ent in the vent cap for these VRLA cells. A deformed pressure relief valve will change ttie operating charactoi^ts of the cell. Temperature high enough to melt the plastics used to compose batteries must be avoided. Another problem found to plague lead acid cells is catalyst poisoning. Precious metal catalysts, such as palladium and platinum are susceptible to poisoning by many chemicals that can limit and negate the effectivoiess of the catalysts. Catalyst poisons can be generated in or found in the battery cells. VRLA batteries are constructed of materials that may exhaust gaseous compounds that are poiscMTOus to catalysts. Such poisons include organic compcRjnds such as pithalates used as a plasticizer in PVC battery jars and covers, and inorganic compounds such as sulfides, mercaptins, amines, stibine and phosphates whose base chemicals can exist as an impurity in battery plates and exhaust as the plates corrode. Amines and mercaptins are used extensively as curing compounds in multi-part epoxies, which are used in the manufacture of cells by many manufacturers. It is also believed that localized areas of high cun-ent densities may cause hydrogen sulfide to form within the cells. Hydrogen sulfide may also be a byproduct of the dry charging process that traps sulfur species in the plates which is then released early in the battery's life. It is believed that compounds such as those described above that have a (-2) state of charge can bond with catalyst activation sites rendering the catalyst ineffective. The catalyst can also be poisoned by large chain molecules, such as phtlhalates, that coat the catalyst substrate and then solidif/ing on it, creating a barrier that prevent the gasses from reaching the catalyst reaction sites. Hydrogen sulfide, SOx species, and other sulfides will also poison precious metal catalysts. It is further believed that simpler and lower cost catalyst devices are desirable. Accordingly, one object of the present invention Is to limit the temperature of the catalytic reaction. Another object of the present invention is to prevent poisoning of the catalyst. Another object is to lower the manufacturing costs of catalyst devices. Summary of the Invention In accordance with the present invoition there is presided a device for combining oxygen and hydrogen gases within a battery cell. The device has a container, which has a chamber. An^nged within the chamber is a catalyst capable of combining oxygen and hydrogen gases to form water vapor. The device includes a micro-porous section having pores through which gases in the battery cell can pass into the chamber to the catalyst. A catalyst poison filter is arranged in the device to remove at least some of the catalyst poisons in the gas passing through the filter to the catalyst. The pore size and developed surface area can be chosen to control the temperature of the catalytic reaction by controlling the amount of gas that can pass through to the catalyst at any given time. The container is preferably made of a non-porous plastic material and has an opening to the chamber. Sealing the opening is the microporous section formed as a microporous member. The filter material here is ideally placed in the chamber between the catalyst and the microporous member. This forces the gas entering the chamber through the microporous member to pass first through the filter before reaching the catalyst and thereby maximizes the effectiveness of the filter. This design presents an embodiment that combines both poison filtering and temperature control in one easy to manufacture, low cost and inherently safe to the cell design. It operates on the principle that the heat of reaction, of the catalyst, can be controlled by limiting the amount of oxygen and hydrogen gas that is exposed to the catalyst. This control is accomplished by selecting the proper pore size, developed and planar surface area, and/or wall thickness of the area that the hydrogen and oxygen pass through in the container that houses the catalyst. This area is created from a porous high temperature acid resistant plastic material that has inherent hydrophobic properties with a porosity that is small enough to not allow a hydrogen flame front to pass through (Anti-Flame Protection). The hydrogen and oxygen gasses will then pass through the filter bed that will remove any catalyst poisons before they reach the active material. Other embodiments of the invention are also provided such as providing the microporous section in the container wall. Brief Description of the Drawings Figure 1 is a cross sectional view of a device in accordance with the present invention having a flange; Figure 1A is an exploded view of the device of Figure 1; Figure 1B is perspective view of the device of Figure 1 attached to a pressure relief vent cap; Figure 2 is a perspective viev/ of a flangless catalyst device held to a pressure relief vent by a holder; Figure 2A is a perspective view of the holder of Figure 2; Figure 2B is a perspective view of the catalyst device of Figure 2; Figure 3 is a top perspective view of a vent boss of a Monoblock type battery cell showing the top of a 1/4 amp embodiment of the invention installed in the vent opening; Figure 3A is an exploded view of the 1/4 amp device of Figure 3; Figure 4 is a frontal view of another embodiment of the catalyst device; Figure 5 is a cross sectional view of another embodiment of the present invention; Figure 6 is a cross sectional view of yet another embodiment of the present invention; Figure 7 is a cross sectional view of another embodiment of the present invention; and Figure 8 is a schematic view of a VRLA battery cell in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION With reference to Figures 1,1A and 1B, a catalyst device 10 is configured for attachment to a pressure relief vent 12 (Figure IB) of the type used with VRLA battery cells. The device 10 has a cylindrically shaped container 14 and is attached to an integral flange 16. The container 14 has a wall 18 defining an internal chamber 22 An opening 20 at the one end of the container 14 permits access to the chamber 22 as described below. The container 14 is preferably made of high temperature plastic material resistant to sulfuric acid and suitable for the internal environment of a battery cell. The container material of this epcibodiment should also be impermeable to liquids and gases so that the gases can enter the chamber 22 only through the opening 20. A preferred material is Questra® made by Dow Chemical. The flange 16 is integral to the container 14 and configured to fit a particular pressure relief vent 12. For pressure relief vents of other manufacturers, a flange configured specifically for the particular vent is readily provided by changing the mold insert in conjunction with the mold for the container 14. Here, the flange is configured to snap to the pressure relief valve 12 as shown. Figure IB, the flange having holes 24 for receiving snap pins 24a of the vent 12. Means of attachment other than a snap type connection may be used. For example, the pins 24a could be non-snap type pins that are inserted into hcrfes 24 of the flange, and then the ends of the pins 24a are melted such as by heat staking or ultra sonic means to fix the container 14 to the pressure relief vent 12. The chamber 22 contains a catalyst 26 for combining oxygen gas and hydrogen gas. Precious metal catalyst such as palladium and platinum may be used, a catalyst 26 of one-half percent palladium impregnated on an activated carbon substrate being preferred for the illustrated embodiment. It is underdood that the uniform spheres representing the catalyst 26 as shown in the drawings are for illustrative purposes, the catalyst capable of being provided in many forms such as granules or fine powder. Positioned between the catalyst 26 and the chamber opening 20, is a poison filter 28 for removing compounds that are poisonous to the catalyst. Suitable filter materials for the type of poisons found in VRLA cells include activated carbon, potassium carbonate (K2CO3), metals such a nickel, ruthenium, copper, and metal salts. A combination of multiple filter materials are preferred as some filter materials have a higher affinity or are more specific to particular poisons. In the illustrated embodiment, a multiple filter bed of 325 mesh activated carbon impregnated with 20% K2CO3 is preferred. For poisons that are basic, the filter materials can be treated by soaking with 1/10 molar HCL (hydrochloric acid) then drying at 180°F for 24 hours to create an acidic filter having a strong affinity to react with basic poisons. For acidic poisons, the filter materials can be treated by soaking with a 5% sodium bicarbonate and water solution then drying at 180°F for 24 hours to create an alkaline filter that will have a stronger affinity to react with acidic poisons. The device 10 has a micro-porous section 30 through which the gas and vapor can pass between the chamber 22 and the environment outside the device 10 (the internal environment of the battery cell). In the present embodiment the micro-porous section 30 takes the form of disk shaped microporous member 30a covering the opening 20 as shown which is fixed on a shoulder 32 formed in the container 14. The microporous disk member 30a is heat sealed or ultrasonically welded in place -see the angled edge 34 where the container was melted as part of the welding or heat staking process. The microporous member 30 is made of a porous material, preferably plastic, such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene) or polypropylene, and which is preferably hydrophobic in nature to water and the electrolyte (sulfuric acid in lead acid cells) in the battery cell. The pore size is such that only gas or vapor can pass through, but liquid will not. Likewise, the microporous section 30 should have a pore size small enough to not allow a hydrogen flame front to pass through. When the microporous member 30a is sealed in place in the opening 10, the catalyst 26 is completely sealed within the chamber 22 such that gas or vapor can pass between the chamber 22 and the environment outside the device 10 only by passing through the pores of the microporous section 30 (disc 30a). The benefit of positioning the filter 28 between the catalyst 26 and microporous disk member 30a is readily seen. Gases entering the chamber 27, which may include compounds poisonous to the catalyst, reach the catalyst only after passing through the filter 28. It is possible to provide a mixture of the catalyst and filter within the chamber 22 rather than the stratified layers shown. Some poisons, however, have a stronger affinity for the catalyst than the filter material, and, where the filter material and catalyst are near each other, may go to and poison the catalyst rather than to the filter. The illustrated embodiment avoids this problem by forcing the poison first through the filter. The present invention also permits control of the heat of reaction in the catalyst by limiting the amount of oxygen and hydrogen gas that is, exposed to the catalyst 26. As previously discussed, the pore size in the microporous section 30 is chosen such that only gas or vapor is capable of passing through, and to also act as an anti-flame barrier. Additionally, in conjunction with other variables such as the planar surface area and the thickness of the miao-porous member 30a the pore size ultimately selected control the amount or rate of gas ttiat can pass into the chamber 22 and subsequentiy be exposed to ttie catalyst 26. This exposure determines the heat of reaction that is generated by the catalyst action of combining the oxygen and the hydrogen gases into water. Pore sizes that are known to work as a method of temperature control are, but not limited to, 1 to 40 microns. Varying the thickness of the micro-porous member 30 in conjunction, with selecting pore size can also be used to control temperature. In the illustrated embodiment of Figures 1, lA, and IB, a preferred configuration has a cylindrical chamber 22 having a volume of approximatEly .35 cubic inches (with internal diameter of .45 inches). The volume of catalyst 26 (1/2% palladium on an activated carbon substrate) is about .12 cubic inches; the volume of filter material 28 (325 mesh activated carbon impregnated with 20% K2CO3) is about .23 cubic inches. The catalyst 26 and filter 28 materials compld:ely fill the chamber 22 and are held tightly within by the micro-porous disk 30a so that there is minimal movement and mixing of the materials even if the device 10 is shaken. It is seen that this CTibodiment has a ratio of 1/3 catalyst to 2/3 filter material by volume. The disk-shaped microporous member 30 is formed of PTFE, 1/8" inch thick, Vi inch diameter, and having a 25 micron pore size. This configuration provides a device 10 rated for about 1 Amp Faraday: 11-12 ml/minutes at standard temperature and pressure of 2 parts H2 and 1 part O2 passing through to the catalyst, and which generate a temperature in the range of 120°F to 140°F at these conditions. In addition to providing temperature and poison cx)ntrol, the present invention also provides a simpler design over previous designs. One previous design us^ a porous ceramic chamber that provided anti-flame protection and which was is externally wrapped with a hydrophobic PTFt film to probat the intenal catalyst from liquid. The PTFE film has a specific prarc^ty that allows hydrogen, oxygen and gaseous water to pass through, but does not allow any liquids to contact the catalyst. The present invention uses technology (the micro-porous section 30) that is inherently hydrophobic, anti-flame preventing, and micro-porous thus eliminating the need for the film and ceramic chamber while still serving the same functions. This results in a simpler and lower cost design. The present invention is also adaptable to the many different battery cells and pressure relief vents of the different manufacturers. As pr^ously discussed, the flange 16 is formed to specifically fit the vent 12 shown in Figure IB. The basic container 14 can be standardized and producai with a mold designed to accept inserts for creating flanges configured to fit vents made by other manufactures. If desired, no flange need be added, the container being retained to the vent by some ottier means. For example, a device 10 having a cylindrical container 14 similar to that shown in Fig. 1 but without the flange 16 is shown in Fig. 2B. The flangless device 10, as shown in Figure 2, is held to the vent 12 of another manufacturer by a holder 36, here a cage type holder as shown in Fig. 2A. The cage holder itself has a flange 38 for attaching to the vent 12, the pins 24b of the vent 12 being inserted in ttie holes 38a and melted to fix the cage 36 with the catalyst device 10 inseted within the cage 36, to the vent 12. For some battery designs it is not possible to attach the catalyst device to the pressure relief vent. Illustrated in Figure 3 is the top view of a jar cover 40 for Monoblock type battery cells that have a vent boss 42 into which a pressure relief valve fits. The vent boss of this particular example has an c^)ening 44, whidi has about a 6 mm diameter, and four recuses 46 around the opening 44. Other vent bosses of other manufacturers may have openings 44 of a different dlam^er. Shown in Figure 3A is a smaller version of the catalyst device 10 having a diam^er (width) no larger than the vent oiDening, in this example about 6 mm, for fitting in the opening 44 of the vent boss 42. The container 14 has a non-porous wall 18 and an cqjening 20 into the chamber 22. In the chamber 22 is a layer of catalyst 26, a layer of filter 28, all of which is sealed from the environment of the battery cdl by the micro-porous section 30 which is formed as a small micro-porous disk membe- 30a. Two tabs 48 integrally connected to the container 14 extend therefriom for fitting into the recesses 46 of the bcss 42 and holding the device 10 in place when installed in the opening 44 as se&n in Figure 3. The configuration shown in Figures 3 and 3A is rated at about 1/4 Amp, the chamber 22 having a volume of about .02 cubic inches, 1/3 to Va of whidi is filled with catalyst 26, the rest witii filter material 28. The micro porous disk member 30a being a PTFE disk of roughly 0.02 inches square surface area, 1/8 inches thick, and a pore size of 25 microns allowing 3-6 ml/minutes at standard temperature and pressure of 2 parts H2 and 1 part O2 passing through to the catalyst. Another optjon would be to simply drop the catalyst d^ice 10 into a battery cell. A configuration suitable for doing so is shown in Figure 4. Here the device 10 has a container 14 similar to that of Figure 1 formed with a series of legs 50 which extend beyond the top end 51 of the container which has ttie micro porous disk member 30a so that no matter how the de/ice 10 lands within the battery cell, the micro porous member 30a will not sit flat against any object which may trfock the flow of gas. With VRUV cells of the Gel type, spitting action within the cell may coat the micro-porous member 30a with gd and block the gas access to the catalyst depending on how the deyice 10 is positioned. A shield could be attached as a separate piece or could be part of the molded container itself to pnDtect the porous hydrophobic disk and the catalyst active material from the spitting silica and silica gel. With non-Gel cells such as AGM and liquid electrolyte cells, this should not be a prdblem. The catalyst cartridge assembly 10 can be m^je to have a self-shutdown mode. If the heat of reaction reaches ttie melting tempoature of the plastic used to house the active material, it will melt and physically cover the active material. This physical covering of the active material will Wock precious m^al activation sites, rendering the catalyst ineffective and shutdown tt»e reaction. It is seen that the use of catalyst is made safer fi-om the viewpoint that by limiting the temperature of the reaction there is no way that a catalyst of this design could possibly damage ttie cell, even If the cell is in a high gassing situation such as boost charge, or a cell failure mode. The catalyst is deigned to bypass excess gas if the cell is creating more gas than tiie catalyst has been deagned to recombine. This reaction limitation is controlled by the porous section 30 which has a predetermined gas flow rate limit. Thus, the present invention can be attached directly to low temperature plastic materials such as polypropylene, ABS and other materials commonly used in batteries. This catalyst can be attached directly to vent caps, or other components of the battery. Another alternative embodiment of the present invention is now described with reference to the device 10 of Figure 5. Unlike the previous embodiment, here, the porous section 30 is in the container wall 18. The device 10 has a cylindrical container 14 having a container wall 18 and defining a chamber 22. An opening 20 provides access to the chamber for adding the catalyst 26. The porous section 30 is provided in at least a section of the wall 18 of the container 14, here the entire wall structure 18 being porous. The container 14 is made of a porous plastic material such as PVDF, Teflon, or Polypropylene. The opening 20 is sealed with a nonporous plug 52 so that the gas or vapor can pass only through the pores in the wall 18. Like the embodiment discussed above, the pore size of the porous section, here the wall 18, is chosen to allow gas to pass, but not liquid, and to prevent a flame front from passing through. Within these parameters, the pore size can be varied to control the amount or rate of gas that can pass through the chamber walls and subsequently be exposed to the catalyst active material, i.e., temperature control. Pore sizes for temperature control are preferably between 1 and 40 microns. Varying the wall thickness of the container in conjunction with the pore size and surface area of the container can also be used to control temperature. The non porous plug 52 is preferably made of an epoxy that does not itself exhaust catalyst poisons and which Is suitable for the environment in battery cells. Such materials include acrylic based compounds such as Loctite Material 3345 which are cured by Ultra Violet radiation for 15 seconds, or sili A thermal mass material 54 may be added vi^ith or without temperature control sized pores to also help control temperature. As seen in Figure 4, the catalyst 26 is mixed with the thermal mass material 54 which can be made of a powder of a ceramic material or a plastic material (e.g., polypropylene, acrylic) or a metal (e.g., aluminum, copper, brass). It is believed that the powdered material should be of a size that is less than or equal to the size of the catalyst material, and that there be about 2 parts thermal mass material to 1 part catalyst material. This design is believed to work by increasing the thermal mass of the chamber, in other words, by spreading the heat of reaction over a larger mass. Catalyst poison filter material 28 can also be added to the device 10 of the type shown in Figure 5. One possibility is to add filter material directly to the plastic material of the container 14. Filter material 28 such as activated carbon can be impregnated into the plastic of the container 14 during the molding process. One way of doing this is to mix the powders of the plastic and the filter materials 28 and then mold the mixture to form the container 14. Pores of the desired size are also added. One example is a mixture of 80% PVDF and 20% activated carbon with K2CO3. The addition of the filter material, however, may lesson the hydrophobic nature of the container. A porous PTFE film wrap around the container 14 as disclosed in U.S. Application Number 09/022,336 could be added if desired to increase the hydrophobic nature. Another possibility (not shown in Figure 5) is to mix the filter material 28 with the catalyst 26 in the chamber 22. As discussed above, however, where poisons are not forced first through a filter, poisons that have a high affinity for the catalyst may still poison the catalyst. Shown itjFigure 6 is a means of adding poison control to a porous ceramic type container. Here a filter material 28 of K 2CO3 is coated onto the outside of the container 14. The ceramic container is dipped in a water solution of dissolved filter material and then dried to leave a coating of filter material. The ceramic container is then wrapped in porous PTFE film 56 which acts as the microporous section 30. Other solvent soluble filter materials may be used as well. Shown iwFigure 7 is a means of adding filter material to any type container by a wrap. A film 58 impregnated with filter material is wrapped around the outside of the container 14 after it is loaded with catalyst 26 and the opening 20 sealed. This film could be laminated to the back of a porous PTFE film, or installed as a separate film which would require a separate porous PTFE film wrap 56 on top. It is seen that an advantageous catalyst device is provided that can be simpler and less costly to produce than previously known devices. Moreover, poison and temperature control functions can be included. The invention also allows for greater flexibility in design of catalyst assemblies to fit a great number of cell designs. For example, the plastic container, whether non-porous or porous, has the advantage of allowing a flange to be added for easy attachment to a pressure relief vent and thereby eliminates the need for holders such as the cage holder even in embodiments where poison and temperature control are not desired. Moreover, the flange can be configured for the relief vent of a particular manufacturer. The catalyst device can be added to a battery cell by itself, attached to a pressure relief vent, or some other means of placing the catalyst in contact with the gasses within a battery cell. A VRLA cell 60 is schematically shown in Figure 8 and has a sealed housing 62, a positive electrode 64 having active material, a negative electrode 66 having active material and which is in spaced relationship to said positive electrode, and an electrolyte in contact with the positive and negative electrodes (normally in the form of plates). The electrolyte may be contained in a separator means so that there is no "free" electrolyte in the cell. The VRLA cell is typically charged on a continuous basis and over a long-term, for example, in excess of five years. The word "continuous" as used herein in connection with the charging of the cell is intended to mean an uninterrupted flow of current, as well as an intermittent flow of current, for example, a pulsating current. A VRLA cell is typically charged at a voltage having a value that is slightly in excess of the value of the open-circuit voltage of the cell which, for example, is typically about 2.15 volts. The term "slightly in excess" means a value no greater than about 0.3 volt above the open circuit voltage of the cell in applications in which there is an intermittent flow of current. In applications in which the flow of current is uninterrupted during charging. it is preferred that the charge voltage have a value that is no greater than about 0.2 volt above the open-circuit voltage of the cell. As discussed above, the catalyst device 10 is ideally attached to the pressure relief vent 12 of the VRLA cell which is positioned in a gas space 68 within the housing where oxygen and hydrogen gas collect. The pressure relief vent 12 allows excess gas to escape the sealed housing and is preferably removable. Thus combining the catalyst device with the relief vent 12 makes the catalyst device removable while assuring it is in contact with the gas for recombination. Parameters and Considerations for Sizing Catalvsts for VRLA Cells It is believe that a standard AGM VRLA cells exhaust 100 ml/day/IOOAh of an oxygen hydrogen mixture at standard VRLA float charging voltages at QCF. It is further believed that similar AGM VRLA cells with catalyst exhaust 20 ml/day/100Ah of pure hydrogen (due to positive plate corrosion) at SO'F. Such gassing data indicates the catalyst must recombine 80 ml/day/IOOAh to keep the negative plates of a VRLA battery fully charged. The minimum amount of Gas to be Combined: The largest AGM VRLA cell currently known to be produced is 1600Ah. Faraday's law states that 1 Amp of current used to breakdown water into stoichiometric Hydrogen and Oxygen gas will produce 11.3 ml/min 2 Hj - 10j at STP. Therefore the catalyst must recombine at most 0.079 amps of gas in a 1600 Ah AGM VRLA cell on float charge at 90^. (1600Ah/100Ah)(80ml/day/100Ah)/((11.3ml/min)(60min/hr)*(24hr/day)). The amount of gas produced by VRLA cells will change with the cell operating temperature based on Arhennius' equation. This equation shows that the volume of gas recombined by the catalyst will increase or decrease by approximately a factor of 2 for every 10'C change in temperature. (lO'C rise in temperature will double the amount of gas needed to recombin'e (80ml/day/100Ah @32T = 160ml/day/1 OOAh @ 42'C)) VRLA cell manufacturers recommend VRLA cells be operated in a climate-controlled environment of TT'F, the SCf used for testing and the above data calculations represents a maximum recombination situation. Heat Generation: The recombination reaction of oxygen and hydrogen to water will create 275 BTU/ft^ of heat. (1ft' of stoichiometric oxy-hydrogen = 28310 ml of gas at STP). Therefore catalysts produce 0.073BTU/min of heat for every 11.3 ml/min (1 amp) of stoichiometric oxy-hydrogen. Maximum Steady State Operating Temperature: This 0.073 Btu/min/amp of heat is dissipated from the catalyst to the surroundings through a combination of heat flow release (conduction, convection, radiation). The micro porous disk of the 1 amp catalyst device 10 is specifically designed (by specifying pore size, surface area, thickness, etc.) to allow 11-12 ml/min stoichiometric oxy-hydrogen gas into the catalyst chamber and the resultant water vapor to diffuse out of the chamber. This specified gas flow rate generates the stated 0.073 BTU/min/amp of heat, which is dissipated by the catalyst to it's surroundings resulting in a steady state operating temperature of 120-140^ measured at the outside surface of the catalyst chamber. There is a similar heat generation to operating temperature relationship for the 0.25 amp catalyst device 10. The geometry of the 0.25 amp catalyst device allows between 3 and 6 ml of stoichiometric oxy-hydrogen into the catalyst with resultant water vapor exiting. The recombination of this amount of oxy-hydrogen generates 0.018 to 0.037 BTU/min of heat. This amount of heat generates a steady state operating temperature of 100-120°F measured on the outside surface the 0.25 amp catalyst chamber. The enthalpy generated by the catalyst reaction is a function of the stoichiometric oxy hydrogen gas flow rate through the micro porous membrane, the-amount of.catalytic material available to react with available gas and the packing density of the catalytic material inside the catalyst chamber. The gas flow rate through the micro porous membrane is a function of membrane pore size, porosity, and surface area perpendicular to gas flow and is an inverse function of membrane thickness (defined as the length of the membrane perpendicular to gas flow). An example of a properly sized micro porous membrane for this application is the preferred embodiment, using a micro porous PTFE disk with a surface area normal to gas flow of: 0.196 in^, a pore size of 25 microns, a porosity of 15% and a thickness perpendicular to gas flow of 0.125in. This size disk limits stoichiometric oxy-hydrogen gas flow to 10-15 ml/min, which limits the enthalpy generated by the catalyst embodiment to 0.064 BTU/min - 0.090 BTU/min. Regarding the filter material, the filters may have a finite life of limited capacity to absorb poisons. Thus over the life of the battery, a filter, or the container with the filter, may need to be replaced. It is understood that the above-identified arrangements are merely illustrative of the many possible specific embodiments which represent applications of the present invention. Numerous and varied other arrangements can readily be devised in accordance with the principles of the invention without departing from the spirit and scope of the invention. We claim, 1. A device for combining gases within a storage battery; comprising: a catalyst container having a container wall and defining an internal chamber; a catalyst arranged within said chamber, said catalyst capable of reacting oxygen gas and hydrogen gas to form water vapour; characterized in that the said device includes a micro-porous section having pores through which said oxygen gas and hydrogen gas can pass between said internal chamber and an outside of said container; and a catalyst poison filter arranged to remove at least a portion of catalyst poisons in said oxygen and hydrogen gas. 2. A device as claimed in claim 1 wherein said micro-porous section is an-anged in at least a portion of said container wall. 3. A device as claimed in claim 2 who-ein said container is made of a plastic material. 4. A device as claimed in claim 3 wherein said micro-porous section has pores sized in the range of about 0.1 to about 400 microns. 5. A device as claimed in claim 3 wheran the material of said poison filter is impregnated into said plastic material. 6. A device as claimed in daim 1 wherein said filter is arranged within said chamber. 7. A device as claimed in claim 6 wherein said filter is arranged in a layer adjacent to said catalyst. 8. A device as claimed in daim 1 wherdn said container is substantially non-porous and has an opening to said chamber, and wherein said miao-porous section comprises a micro-porous hydrophobic member arranged to seal said opening and having pores of a size to allow gas to pass there through to said chamber 9. A device as claimed in claim 1 wherein said catalyst poison filter is made of activated carbon. 10. A device as claimed in claim 1 wherein said poison filter comprises potassium carbonate. 11. A device as claimed in claim 9 wherein said activated carbon is impregnated with potassium carbonate. 12. A device as claimed in claim 10 wherein said activated cariDon is impregnated with potassium carbonate. 13. A device as claimed in claim 1 comprising a pressure relief vent. 14. A device as claimed in claim 1 wherein said container is made of a plastic material and is attached to a flange capable of attaching to a pressure relief vent. 15. A device for combining gases in a storage battery; comprising: a catalyst container having an internal chamber and an opening to said chamber, said container being substantially non-porous; a catalyst arranged within said chamber, said cataly^ capable of reacting oxygen gas and hydrogen gas; characterized in that the said device include a catalyst poison filter an-anged witJiln said chamba-; and a micro-porous hydrophobic member arranged to seal said opening, said micro-porous member having por^ of suitable size to permit gas to pass there through while being a barrier to liquids. 16. A device for combining gases as claimed in claim 15 wherein said filter is arranged between said catalyst and said micro-porous member. 17. A device for combining gases as claimed claim 16 wherein said container is made of a plastic material. 18. A device for combining gases as claimed in claim 15 wherein said miao-porous member comprises a plastic material. 19. A device for combining gases as claimed in claim 15 wherein said container is cylindrical, has no more than one said opening, and comprises a plastic material, and wherein said micro-porous member comprises a plastic material. 20. A device for combining gases as claimed in claim 15 comprising a pressure relief vent, said container being attachaJ to said pressure rei\df vent. 21. A device for combining gases as claimed in claim 15 wherein said container is made of a plastic material and is attached to a flange capable of attaching to a pressure relief vent. 22. A device for combining gases as claimed in claim 20 wherein said container is supported in a holder attached to said vent. 23. A device for combing gases as claim«l in claim 15 comprising at least one tab extending from said container, said tab capable of engaging a complementary recess for holding said housing in place when installed in said storage battery. 24. A device for combining gases as claimed in claim 20 wherein said housing is snap connected to said vent cap. 25. A value regulated lead acid (VRLA) battery cell comprising: a sealed housing; a positive electrode positioned in the housing; a negative electrode positioned in the housing in spaced relationship from the positive electrode; and electrolyte in said housing in contact with said positive and negative electrodes; a gas space within said housing in which oxygen and hydrogen gas collects; a pressure relief vent which allows gas to escape from the housing and which prevents oxygen gas ftx)m outside the housing to contact said negative electrode; a catalyst device an-anged to be in contact with at least a portion of said oxygen and hydrogen gas, said device including a container having a container wall and defining an internal chamber, and a catalyst arranged within said chamber, said catalyst capable of reacting oxygen gas and hydrogen gas to form water vapour; characterized in that said battery cell includes a catalyst poison filter arrangol to be in contact with at least a portion of said oxygen and hydrogen gas. 26. A VRLA battery cell as claimed in claim 25 wherein said catalyst device comprises a micro-porous section arranged to and having pores sized to allow oxygen gas and hydrogen gas to pass from said gas space to said chamber, said micro- porous section being hydrophobic to said electrolyte. 27. A VRLA battery cell as claimed in daim 26 wheran said poison filter is arranged within said chamber, and said micro-porous hydrophobic section comprises a single piece of plastic material. 28. A catalyst container for use in battery cells having an electrolyte characterized in that said container including: a container wall comprising a plastic material; a chamber within said container capable of holding catalyst; and a flange attached to said container. 29. A container as claimed in claim 28 whaein said container wall has pores of sufiRcient size to allow gas to pass through to sakj chamber, and is hydrophobic to said electrolyte. 30. A container as claimed in claim 28 wha'ein said container wall is impermeable to gas and liquids, and furttier includes an opening into said chamber, said opening being sealed with a micro-porous hydrophobic member having pores of sufficient size to allow gas to pass through to said chamber. 31. In a method for float charging a valve-regulated, lead-acid (VRLA) cell (60) at a charge voltage, which has a value that is slightly in esccess of the value of the open circuit voltage of ttie cell; said cell (60) including, in spaced-apart relationship, a positive electrode (64) and a negative electrode (66) electrolyte in contact with said positive and negative electrodes (64, 66), and a catalyst (26) for combining oxygen and hydrogen gases to fonn water vapor; wherein during charging of the cell, there is (a) a self-discharge reaction at the negative electrode (64), (b) the production at the positive and negative electrodes (64, 66) respectively of oxygen and hydrogen gases, and (c) the exothermic conversion by said catalyst of a portion of the oxygen and hydrogen gases to water; the improvemait comprising reducing the rate at which said oxygen and hydrogen gases that are produced contact said catalyst (26) to reduce the rate at which heat is generated by said exothermic conversion of said gases to water. 32. The method as claimed in claim 31, comprises the step of filtering said gases to remove any catalyst poisons before said gases contact said catalyst (26). 33. A device (10) for combining gas^ within a storage battery (60); comprising: a catalyst container (14) having a container wall (18) and defining an Internal chamber (22); a catalyst (26) arranged within said chamber (22), said catalyst (26) capable of reacting oxygen gas and hydrogen gas to form water vapor; and a micro-porous section (30) having por^ through which said oxygen gas and hydrogen gas can pass into said internal chamber (22) from outside of said container (14); wherein at least one of the pore size, planar surface area and thickness of said micro-porous member (30) is selected to control the amount or rate at which said oxygen and hydrogen gases can pass into said internal diamber (22) to control the heat generated by the catalytic combination of said oxygen and hydrogen gases. 34. A device as claimed in claim 33 wherein said micro-porous section (30) is arranged in at least a portion of said container wall (18). 35. A device as claimed in claim 33 wherein said container (14) comprises a plastics material. 36. A device as claimed in claim 33 wherein said micro-porous section (30) has pores ranging in size between 1 and 40 microns. 37. A device as claimed in claim 33 wherein said container (14) is substantially non-porous and has an opening (20) to said chamber, and wherein said micro-porous section (30) comprises a micro-porous hydrc^oblc member arranged to seal said opening and having pores of a size to allow gas to pass there through to said chamber (22). 38. A device as claimed in claim 33 flirther comprising a pressure relief vent (12). 39. A device as claimed in claim 33 wherein said container (14) is made of a plastic material and is attached to a flange (16) capable of attaching to a pressure relief vent.

Full Text

This application claims the benefit of U.S. Provisional Applications Numbers 60/112,305 filed December 14, 1998, 50/113,579 filed December 24,1998, and 50/148,536 filed August 12,1999, all of which are hereby incorporated by reference.
BACKGROUND
1. Field of the Invention
The present invention relates to the use of catalysts for improving the service life of valve regulated lead acid (VRLA) cells, and to a catalyst device which may also be applicable to other types of batteries where it is desirable to recombine excess oxygen with hydrogen produced in the battery cell. More particularly, the present invention relates to improved catalyst devices that minimize catalyst poisoning and control the temperature of the catalytic reaction.
2. Background of the Invention
Significant improvements to VRLA battery cells can be made with the addition of a catalyst for recombining oxygen and hydrogen gasses within the cells as disclosed in U.S. Application Number 09/022,336 filed 2/11/98, and virtiich is hereby incorporated by reference. One preferred method of adding catalyst to VRLA cells is to couple the catalyst with the pressure relief vent, i.e., the "valve", which provides a convenient means of retrofitting existing cells as well adding catalyst to new cells. A novel catalyst device for use with pressure relief vents is disclosed in U.S. Application Number 09/022,336. While the addition of catalyst provides significant improvement in the performance and of life of VRLA^cells, additional improvements to the catalyst itself, particularly with the structures and devices that support or house the catalyst, are believed necessary to gain the full benefits of the catalyst.
High rates of gassing in VRLA battery cells can be caused by conditions such as thermal runaway, malfunctioning power rectifiers, boost charging, charging at

abnormally high rates of voltage, and other reasons known in the art. In lead-acid battery cells, oxygen and hydrogen gas is generated due to the electrolysis of water. If a catalyst was installed in a cell experiencing a high rate of gas production, the catalyst would catalyze the oxygen arKi hydrogen to water in a highly exothermic reaction. The resulting enthalpy could generate enough heat to melt many commonly used plastic materials that compose the battery cover, jar or vent cap assemblies. This high reaction temperature can also limit the materials that can be used to house the active catalytic material.
One catalyst device as described in the above referenced U.S. Patent Application Number 09/022,336, uses a porous ceramic cartridge to house the catalytic active material. This porous cartridge allows gas to enter the diamber and water vapor to exit the chamber, and prevents the passing of a flame from inside the chamber to outside the chamber if developed due to ignition of the gas^. The temperature achieved, as a result of the exothermic reaction, is governed mainly by the amount of gas produced by the battery. In the normal functioning of a VRLA battery, tiie temperature of reaction is generally not more than 5** to 10**F above ambient temp»Bture. However, in the case of high rates of gassing, a higher than normal temperature could occur which could lead to melting of the plastic that supports the catalyst cartridge, that composes the vent cap or that composes the cell jar or cell cover. The high tanpeature could also defonm the pressure relief valve that is pr^ent in the vent cap for these VRLA cells. A deformed pressure relief valve will change ttie operating charactoi^ts of the cell. Temperature high enough to melt the plastics used to compose batteries must be avoided.
Another problem found to plague lead acid cells is catalyst poisoning. Precious metal catalysts, such as palladium and platinum are susceptible to poisoning by many chemicals that can limit and negate the effectivoiess of the catalysts. Catalyst poisons can be generated in or found in the battery cells. VRLA batteries are constructed of materials that may exhaust gaseous compounds that are poiscMTOus to catalysts. Such poisons include organic compcRjnds such as pithalates used as a plasticizer in PVC battery jars and covers, and inorganic compounds such as sulfides, mercaptins, amines, stibine and phosphates whose base chemicals can exist as an impurity in battery plates

and exhaust as the plates corrode. Amines and mercaptins are used extensively as curing compounds in multi-part epoxies, which are used in the manufacture of cells by many manufacturers. It is also believed that localized areas of high cun-ent densities may cause hydrogen sulfide to form within the cells. Hydrogen sulfide may also be a byproduct of the dry charging process that traps sulfur species in the plates which is then released early in the battery's life. It is believed that compounds such as those described above that have a (-2) state of charge can bond with catalyst activation sites rendering the catalyst ineffective. The catalyst can also be poisoned by large chain molecules, such as phtlhalates, that coat the catalyst substrate and then solidif/ing on it, creating a barrier that prevent the gasses from reaching the catalyst reaction sites. Hydrogen sulfide, SOx species, and other sulfides will also poison precious metal catalysts.
It is further believed that simpler and lower cost catalyst devices are desirable.
Accordingly, one object of the present invention Is to limit the temperature of the catalytic reaction.
Another object of the present invention is to prevent poisoning of the catalyst.
Another object is to lower the manufacturing costs of catalyst devices.
Summary of the Invention
In accordance with the present invoition there is presided a device for combining oxygen and hydrogen gases within a battery cell. The device has a container, which has a chamber. An^nged within the chamber is a catalyst capable of combining oxygen and hydrogen gases to form water vapor. The device includes a micro-porous section having pores through which gases in the battery cell can pass into the chamber to the catalyst. A catalyst poison filter is arranged in the device to remove at least some of the catalyst poisons in the gas passing through the filter to the catalyst.

The pore size and developed surface area can be chosen to control the temperature of the catalytic reaction by controlling the amount of gas that can pass through to the catalyst at any given time.
The container is preferably made of a non-porous plastic material and has an opening to the chamber. Sealing the opening is the microporous section formed as a microporous member. The filter material here is ideally placed in the chamber between the catalyst and the microporous member. This forces the gas entering the chamber through the microporous member to pass first through the filter before reaching the catalyst and thereby maximizes the effectiveness of the filter. This design presents an embodiment that combines both poison filtering and temperature control in one easy to manufacture, low cost and inherently safe to the cell design. It operates on the principle that the heat of reaction, of the catalyst, can be controlled by limiting the amount of oxygen and hydrogen gas that is exposed to the catalyst. This control is accomplished by selecting the proper pore size, developed and planar surface area, and/or wall thickness of the area that the hydrogen and oxygen pass through in the container that houses the catalyst. This area is created from a porous high temperature acid resistant plastic material that has inherent hydrophobic properties with a porosity that is small enough to not allow a hydrogen flame front to pass through (Anti-Flame Protection). The hydrogen and oxygen gasses will then pass through the filter bed that will remove any catalyst poisons before they reach the active material.
Other embodiments of the invention are also provided such as providing the microporous section in the container wall.
Brief Description of the Drawings
Figure 1 is a cross sectional view of a device in accordance with the present invention having a flange;
Figure 1A is an exploded view of the device of Figure 1;
Figure 1B is perspective view of the device of Figure 1 attached to a pressure relief vent cap;

Figure 2 is a perspective viev/ of a flangless catalyst device held to a pressure relief vent by a holder;
Figure 2A is a perspective view of the holder of Figure 2;
Figure 2B is a perspective view of the catalyst device of Figure 2;
Figure 3 is a top perspective view of a vent boss of a Monoblock type battery cell showing the top of a 1/4 amp embodiment of the invention installed in the vent opening;
Figure 3A is an exploded view of the 1/4 amp device of Figure 3;
Figure 4 is a frontal view of another embodiment of the catalyst device;
Figure 5 is a cross sectional view of another embodiment of the present invention;
Figure 6 is a cross sectional view of yet another embodiment of the present invention;
Figure 7 is a cross sectional view of another embodiment of the present invention; and
Figure 8 is a schematic view of a VRLA battery cell in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION With reference to Figures 1,1A and 1B, a catalyst device 10 is configured for attachment to a pressure relief vent 12 (Figure IB) of the type used with VRLA battery cells. The device 10 has a cylindrically shaped container 14 and is attached to an integral flange 16. The container 14 has a wall 18 defining an internal chamber 22 An opening 20 at the one end of the container 14 permits access to the chamber 22 as described below. The container 14 is preferably made of high temperature plastic material resistant to sulfuric acid and suitable for the internal environment of a battery cell. The container material of this epcibodiment should also be impermeable to liquids and gases so that the gases can enter the chamber 22 only through the opening 20. A preferred material is Questra® made by Dow Chemical.

The flange 16 is integral to the container 14 and configured to fit a particular pressure relief vent 12. For pressure relief vents of other manufacturers, a flange configured specifically for the particular vent is readily provided by changing the mold insert in conjunction with the mold for the container 14. Here, the flange is configured to snap to the pressure relief valve 12 as shown. Figure IB, the flange having holes 24 for receiving snap pins 24a of the vent 12. Means of attachment other than a snap type connection may be used. For example, the pins 24a could be non-snap type pins that are inserted into hcrfes 24 of the flange, and then the ends of the pins 24a are melted such as by heat staking or ultra sonic means to fix the container 14 to the pressure relief vent 12.
The chamber 22 contains a catalyst 26 for combining oxygen gas and hydrogen gas. Precious metal catalyst such as palladium and platinum may be used, a catalyst 26 of one-half percent palladium impregnated on an activated carbon substrate being preferred for the illustrated embodiment. It is underdood that the uniform spheres representing the catalyst 26 as shown in the drawings are for illustrative purposes, the catalyst capable of being provided in many forms such as granules or fine powder.
Positioned between the catalyst 26 and the chamber opening 20, is a poison filter 28 for removing compounds that are poisonous to the catalyst. Suitable filter materials for the type of poisons found in VRLA cells include activated carbon, potassium carbonate (K2CO3), metals such a nickel, ruthenium, copper, and metal salts. A combination of multiple filter materials are preferred as some filter materials have a higher affinity or are more specific to particular poisons. In the illustrated embodiment, a multiple filter bed of 325 mesh activated carbon impregnated with 20% K2CO3 is preferred.
For poisons that are basic, the filter materials can be treated by soaking with 1/10 molar HCL (hydrochloric acid) then drying at 180°F for 24 hours to create an acidic filter having a strong affinity to react with basic poisons. For acidic poisons, the filter materials can be treated by soaking with a 5% sodium bicarbonate and water solution then drying at 180°F for 24 hours to create an alkaline filter that will have a stronger affinity to react with acidic poisons.

The device 10 has a micro-porous section 30 through which the gas and vapor can pass between the chamber 22 and the environment outside the device 10 (the internal environment of the battery cell). In the present embodiment the micro-porous section 30 takes the form of disk shaped microporous member 30a covering the opening 20 as shown which is fixed on a shoulder 32 formed in the container 14. The microporous disk member 30a is heat sealed or ultrasonically welded in place -see the angled edge 34 where the container was melted as part of the welding or heat staking process. The microporous member 30 is made of a porous material, preferably plastic, such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene) or polypropylene, and which is preferably hydrophobic in nature to water and the electrolyte (sulfuric acid in lead acid cells) in the battery cell. The pore size is such that only gas or vapor can pass through, but liquid will not. Likewise, the microporous section 30 should have a pore size small enough to not allow a hydrogen flame front to pass through. When the microporous member 30a is sealed in place in the opening 10, the catalyst 26 is completely sealed within the chamber 22 such that gas or vapor can pass between the chamber 22 and the environment outside the device 10 only by passing through the pores of the microporous section 30 (disc 30a).
The benefit of positioning the filter 28 between the catalyst 26 and microporous disk member 30a is readily seen. Gases entering the chamber 27, which may include compounds poisonous to the catalyst, reach the catalyst only after passing through the filter 28. It is possible to provide a mixture of the catalyst and filter within the chamber 22 rather than the stratified layers shown. Some poisons, however, have a stronger affinity for the catalyst than the filter material, and, where the filter material and catalyst are near each other, may go to and poison the catalyst rather than to the filter. The illustrated embodiment avoids this problem by forcing the poison first through the filter.
The present invention also permits control of the heat of reaction in the catalyst by limiting the amount of oxygen and hydrogen gas that is, exposed to the catalyst 26. As previously discussed, the pore size in the microporous section 30 is chosen such that only gas or vapor is capable of passing through, and to also act as

an anti-flame barrier. Additionally, in conjunction with other variables such as the planar surface area and the thickness of the miao-porous member 30a the pore size ultimately selected control the amount or rate of gas ttiat can pass into the chamber 22 and subsequentiy be exposed to ttie catalyst 26. This exposure determines the heat of reaction that is generated by the catalyst action of combining the oxygen and the hydrogen gases into water. Pore sizes that are known to work as a method of temperature control are, but not limited to, 1 to 40 microns. Varying the thickness of the micro-porous member 30 in conjunction, with selecting pore size can also be used to control temperature.
In the illustrated embodiment of Figures 1, lA, and IB, a preferred configuration has a cylindrical chamber 22 having a volume of approximatEly .35 cubic inches (with internal diameter of .45 inches). The volume of catalyst 26 (1/2% palladium on an activated carbon substrate) is about .12 cubic inches; the volume of filter material 28 (325 mesh activated carbon impregnated with 20% K2CO3) is about .23 cubic inches. The catalyst 26 and filter 28 materials compld:ely fill the chamber 22 and are held tightly within by the micro-porous disk 30a so that there is minimal movement and mixing of the materials even if the device 10 is shaken. It is seen that this CTibodiment has a ratio of 1/3 catalyst to 2/3 filter material by volume.
The disk-shaped microporous member 30 is formed of PTFE, 1/8" inch thick, Vi inch diameter, and having a 25 micron pore size. This configuration provides a device 10 rated for about 1 Amp Faraday: 11-12 ml/minutes at standard temperature and pressure of 2 parts H2 and 1 part O2 passing through to the catalyst, and which generate a temperature in the range of 120°F to 140°F at these conditions.
In addition to providing temperature and poison cx)ntrol, the present invention also provides a simpler design over previous designs. One previous design us^ a porous ceramic chamber that provided anti-flame protection and which was is externally wrapped with a hydrophobic PTFt film to probat the intenal catalyst from liquid. The PTFE film has a specific prarc^ty that allows hydrogen, oxygen and gaseous water to pass through, but does not allow any liquids to contact the catalyst. The present invention uses technology (the micro-porous section 30) that is inherently hydrophobic, anti-flame preventing, and micro-porous thus eliminating the need for the film and

ceramic chamber while still serving the same functions. This results in a simpler and lower cost design.
The present invention is also adaptable to the many different battery cells and pressure relief vents of the different manufacturers. As pr^ously discussed, the flange 16 is formed to specifically fit the vent 12 shown in Figure IB. The basic container 14 can be standardized and producai with a mold designed to accept inserts for creating flanges configured to fit vents made by other manufactures. If desired, no flange need be added, the container being retained to the vent by some ottier means. For example, a device 10 having a cylindrical container 14 similar to that shown in Fig. 1 but without the flange 16 is shown in Fig. 2B. The flangless device 10, as shown in Figure 2, is held to the vent 12 of another manufacturer by a holder 36, here a cage type holder as shown in Fig. 2A. The cage holder itself has a flange 38 for attaching to the vent 12, the pins 24b of the vent 12 being inserted in ttie holes 38a and melted to fix the cage 36 with the catalyst device 10 inseted within the cage 36, to the vent 12.
For some battery designs it is not possible to attach the catalyst device to the pressure relief vent. Illustrated in Figure 3 is the top view of a jar cover 40 for Monoblock type battery cells that have a vent boss 42 into which a pressure relief valve fits. The vent boss of this particular example has an c^)ening 44, whidi has about a 6 mm diameter, and four recuses 46 around the opening 44. Other vent bosses of other manufacturers may have openings 44 of a different dlam^er. Shown in Figure 3A is a smaller version of the catalyst device 10 having a diam^er (width) no larger than the vent oiDening, in this example about 6 mm, for fitting in the opening 44 of the vent boss 42. The container 14 has a non-porous wall 18 and an cqjening 20 into the chamber 22. In the chamber 22 is a layer of catalyst 26, a layer of filter 28, all of which is sealed from the environment of the battery cdl by the micro-porous section 30 which is formed as a small micro-porous disk membe- 30a. Two tabs 48 integrally connected to the container 14 extend therefriom for fitting into the recesses 46 of the bcss 42 and holding the device 10 in place when installed in the opening 44 as se&n in Figure 3.

The configuration shown in Figures 3 and 3A is rated at about 1/4 Amp, the chamber 22 having a volume of about .02 cubic inches, 1/3 to Va of whidi is filled with catalyst 26, the rest witii filter material 28. The micro porous disk member 30a being a PTFE disk of roughly 0.02 inches square surface area, 1/8 inches thick, and a pore size of 25 microns allowing 3-6 ml/minutes at standard temperature and pressure of 2 parts H2 and 1 part O2 passing through to the catalyst.
Another optjon would be to simply drop the catalyst d^ice 10 into a battery cell. A configuration suitable for doing so is shown in Figure 4. Here the device 10 has a container 14 similar to that of Figure 1 formed with a series of legs 50 which extend beyond the top end 51 of the container which has ttie micro porous disk member 30a so that no matter how the de/ice 10 lands within the battery cell, the micro porous member 30a will not sit flat against any object which may trfock the flow of gas.
With VRUV cells of the Gel type, spitting action within the cell may coat the micro-porous member 30a with gd and block the gas access to the catalyst depending on how the deyice 10 is positioned. A shield could be attached as a separate piece or could be part of the molded container itself to pnDtect the porous hydrophobic disk and the catalyst active material from the spitting silica and silica gel. With non-Gel cells such as AGM and liquid electrolyte cells, this should not be a prdblem.
The catalyst cartridge assembly 10 can be m^je to have a self-shutdown mode. If the heat of reaction reaches ttie melting tempoature of the plastic used to house the active material, it will melt and physically cover the active material. This physical covering of the active material will Wock precious m^al activation sites, rendering the catalyst ineffective and shutdown tt»e reaction.
It is seen that the use of catalyst is made safer fi-om the viewpoint that by limiting the temperature of the reaction there is no way that a catalyst of this design could possibly damage ttie cell, even If the cell is in a high gassing situation such as boost charge, or a cell failure mode. The catalyst is deigned to bypass excess gas if the cell is creating more gas than tiie catalyst has been deagned to recombine.

This reaction limitation is controlled by the porous section 30 which has a predetermined gas flow rate limit.
Thus, the present invention can be attached directly to low temperature plastic materials such as polypropylene, ABS and other materials commonly used in batteries. This catalyst can be attached directly to vent caps, or other components of the battery.
Another alternative embodiment of the present invention is now described with reference to the device 10 of Figure 5. Unlike the previous embodiment, here, the porous section 30 is in the container wall 18. The device 10 has a cylindrical container 14 having a container wall 18 and defining a chamber 22. An opening 20 provides access to the chamber for adding the catalyst 26. The porous section 30 is provided in at least a section of the wall 18 of the container 14, here the entire wall structure 18 being porous. The container 14 is made of a porous plastic material such as PVDF, Teflon, or Polypropylene. The opening 20 is sealed with a nonporous plug 52 so that the gas or vapor can pass only through the pores in the wall 18. Like the embodiment discussed above, the pore size of the porous section, here the wall 18, is chosen to allow gas to pass, but not liquid, and to prevent a flame front from passing through. Within these parameters, the pore size can be varied to control the amount or rate of gas that can pass through the chamber walls and subsequently be exposed to the catalyst active material, i.e., temperature control. Pore sizes for temperature control are preferably between 1 and 40 microns. Varying the wall thickness of the container in conjunction with the pore size and surface area of the container can also be used to control temperature.
The non porous plug 52 is preferably made of an epoxy that does not itself exhaust catalyst poisons and which Is suitable for the environment in battery cells. Such materials include acrylic based compounds such as Loctite Material 3345 which are cured by Ultra Violet radiation for 15 seconds, or sili
A thermal mass material 54 may be added vi^ith or without temperature control sized pores to also help control temperature. As seen in Figure 4, the catalyst 26 is mixed with the thermal mass material 54 which can be made of a powder of a ceramic material or a plastic material (e.g., polypropylene, acrylic) or a metal (e.g., aluminum, copper, brass). It is believed that the powdered material should be of a size that is less than or equal to the size of the catalyst material, and that there be about 2 parts thermal mass material to 1 part catalyst material. This design is believed to work by increasing the thermal mass of the chamber, in other words, by spreading the heat of reaction over a larger mass.
Catalyst poison filter material 28 can also be added to the device 10 of the type shown in Figure 5. One possibility is to add filter material directly to the plastic material of the container 14. Filter material 28 such as activated carbon can be impregnated into the plastic of the container 14 during the molding process. One way of doing this is to mix the powders of the plastic and the filter materials 28 and then mold the mixture to form the container 14. Pores of the desired size are also added. One example is a mixture of 80% PVDF and 20% activated carbon with K2CO3. The addition of the filter material, however, may lesson the hydrophobic nature of the container. A porous PTFE film wrap around the container 14 as disclosed in U.S. Application Number 09/022,336 could be added if desired to increase the hydrophobic nature.
Another possibility (not shown in Figure 5) is to mix the filter material 28 with the catalyst 26 in the chamber 22. As discussed above, however, where poisons are not forced first through a filter, poisons that have a high affinity for the catalyst may still poison the catalyst.
Shown itjFigure 6 is a means of adding poison control to a porous ceramic type container. Here a filter material 28 of K 2CO3 is coated onto the outside of the container 14. The ceramic container is dipped in a water solution of dissolved filter material and then dried to leave a coating of filter material. The ceramic container is then wrapped in porous PTFE film 56 which acts as the microporous section 30. Other solvent soluble filter materials may be used as well.

Shown iwFigure 7 is a means of adding filter material to any type container by a wrap. A film 58 impregnated with filter material is wrapped around the outside of the container 14 after it is loaded with catalyst 26 and the opening 20 sealed. This film could be laminated to the back of a porous PTFE film, or installed as a separate film which would require a separate porous PTFE film wrap 56 on top.
It is seen that an advantageous catalyst device is provided that can be simpler and less costly to produce than previously known devices. Moreover, poison and temperature control functions can be included. The invention also allows for greater flexibility in design of catalyst assemblies to fit a great number of cell designs. For example, the plastic container, whether non-porous or porous, has the advantage of allowing a flange to be added for easy attachment to a pressure relief vent and thereby eliminates the need for holders such as the cage holder even in embodiments where poison and temperature control are not desired. Moreover, the flange can be configured for the relief vent of a particular manufacturer.
The catalyst device can be added to a battery cell by itself, attached to a pressure relief vent, or some other means of placing the catalyst in contact with the gasses within a battery cell. A VRLA cell 60 is schematically shown in Figure 8 and has a sealed housing 62, a positive electrode 64 having active material, a negative electrode 66 having active material and which is in spaced relationship to said positive electrode, and an electrolyte in contact with the positive and negative electrodes (normally in the form of plates). The electrolyte may be contained in a separator means so that there is no "free" electrolyte in the cell. The VRLA cell is typically charged on a continuous basis and over a long-term, for example, in excess of five years. The word "continuous" as used herein in connection with the charging of the cell is intended to mean an uninterrupted flow of current, as well as an intermittent flow of current, for example, a pulsating current. A VRLA cell is typically charged at a voltage having a value that is slightly in excess of the value of the open-circuit voltage of the cell which, for example, is typically about 2.15 volts. The term "slightly in excess" means a value no greater than about 0.3 volt above the open circuit voltage of the cell in applications in which there is an intermittent flow of current. In applications in which the flow of current is uninterrupted during charging.

it is preferred that the charge voltage have a value that is no greater than about 0.2 volt above the open-circuit voltage of the cell. As discussed above, the catalyst device 10 is ideally attached to the pressure relief vent 12 of the VRLA cell which is positioned in a gas space 68 within the housing where oxygen and hydrogen gas collect. The pressure relief vent 12 allows excess gas to escape the sealed housing and is preferably removable. Thus combining the catalyst device with the relief vent 12 makes the catalyst device removable while assuring it is in contact with the gas for recombination.
Parameters and Considerations for Sizing Catalvsts for VRLA Cells
It is believe that a standard AGM VRLA cells exhaust 100 ml/day/IOOAh of an oxygen hydrogen mixture at standard VRLA float charging voltages at QCF. It is further believed that similar AGM VRLA cells with catalyst exhaust 20 ml/day/100Ah of pure hydrogen (due to positive plate corrosion) at SO'F. Such gassing data indicates the catalyst must recombine 80 ml/day/IOOAh to keep the negative plates of a VRLA battery fully charged.
The minimum amount of Gas to be Combined: The largest AGM VRLA cell currently known to be produced is 1600Ah. Faraday's law states that 1 Amp of current used to breakdown water into stoichiometric Hydrogen and Oxygen gas will produce 11.3 ml/min 2 Hj - 10j at STP. Therefore the catalyst must recombine at most 0.079 amps of gas in a 1600 Ah AGM VRLA cell on float charge at 90^. (1600Ah/100Ah)*(80ml/day/100Ah)/((11.3ml/min)*(60min/hr)*(24hr/day)).
The amount of gas produced by VRLA cells will change with the cell operating temperature based on Arhennius' equation. This equation shows that the volume of gas recombined by the catalyst will increase or decrease by approximately a factor of 2 for every 10'C change in temperature. (lO'C rise in temperature will double the amount of gas needed to recombin'e (80ml/day/100Ah @32T = 160ml/day/1 OOAh @ 42'C))
VRLA cell manufacturers recommend VRLA cells be operated in a climate-controlled environment of TT'F, the SCf used for testing and the above data calculations represents a maximum recombination situation.

Heat Generation: The recombination reaction of oxygen and hydrogen to water will create 275 BTU/ft^ of heat. (1ft' of stoichiometric oxy-hydrogen = 28310 ml of gas at STP). Therefore catalysts produce 0.073BTU/min of heat for every 11.3 ml/min (1 amp) of stoichiometric oxy-hydrogen.
Maximum Steady State Operating Temperature: This 0.073 Btu/min/amp of heat is dissipated from the catalyst to the surroundings through a combination of heat flow release (conduction, convection, radiation). The micro porous disk of the 1 amp catalyst device 10 is specifically designed (by specifying pore size, surface area, thickness, etc.) to allow 11-12 ml/min stoichiometric oxy-hydrogen gas into the catalyst chamber and the resultant water vapor to diffuse out of the chamber. This specified gas flow rate generates the stated 0.073 BTU/min/amp of heat, which is dissipated by the catalyst to it's surroundings resulting in a steady state operating temperature of 120-140^ measured at the outside surface of the catalyst chamber.
There is a similar heat generation to operating temperature relationship for the 0.25 amp catalyst device 10. The geometry of the 0.25 amp catalyst device allows between 3 and 6 ml of stoichiometric oxy-hydrogen into the catalyst with resultant water vapor exiting. The recombination of this amount of oxy-hydrogen generates 0.018 to 0.037 BTU/min of heat. This amount of heat generates a steady state operating temperature of 100-120°F measured on the outside surface the 0.25 amp catalyst chamber.
The enthalpy generated by the catalyst reaction is a function of the stoichiometric oxy hydrogen gas flow rate through the micro porous membrane, the-amount of.catalytic material available to react with available gas and the packing density of the catalytic material inside the catalyst chamber.
The gas flow rate through the micro porous membrane is a function of membrane pore size, porosity, and surface area perpendicular to gas flow and is an inverse function of membrane thickness (defined as the length of the membrane perpendicular to gas flow).
An example of a properly sized micro porous membrane for this application is the preferred embodiment, using a micro porous PTFE disk with a surface area normal to gas flow of: 0.196 in^, a pore size of 25 microns, a porosity of 15% and a

thickness perpendicular to gas flow of 0.125in. This size disk limits stoichiometric oxy-hydrogen gas flow to 10-15 ml/min, which limits the enthalpy generated by the catalyst embodiment to 0.064 BTU/min - 0.090 BTU/min.
Regarding the filter material, the filters may have a finite life of limited capacity to absorb poisons. Thus over the life of the battery, a filter, or the container with the filter, may need to be replaced.
It is understood that the above-identified arrangements are merely illustrative of the many possible specific embodiments which represent applications of the present invention. Numerous and varied other arrangements can readily be devised in accordance with the principles of the invention without departing from the spirit and scope of the invention.

We claim,
1. A device for combining gases within a storage battery; comprising:
a catalyst container having a container wall and defining an internal chamber;
a catalyst arranged within said chamber, said catalyst capable of reacting oxygen gas and hydrogen gas to form water vapour;
characterized in that the said device includes
a micro-porous section having pores through which said oxygen gas and hydrogen gas can pass between said internal chamber and an outside of said container; and
a catalyst poison filter arranged to remove at least a portion of catalyst poisons in said oxygen and hydrogen gas.
2. A device as claimed in claim 1 wherein said micro-porous section is an-anged in at least a portion of said container wall.
3. A device as claimed in claim 2 who-ein said container is made of a plastic material.
4. A device as claimed in claim 3 wherein said micro-porous section has pores sized in the range of about 0.1 to about 400 microns.
5. A device as claimed in claim 3 wheran the material of said poison filter is impregnated into said plastic material.
6. A device as claimed in daim 1 wherein said filter is arranged within said chamber.
7. A device as claimed in claim 6 wherein said filter is arranged in a layer adjacent to said catalyst.
8. A device as claimed in daim 1 wherdn said container is substantially non-porous and has an opening to said chamber, and wherein said miao-porous section comprises a micro-porous hydrophobic member arranged to seal said opening and having pores of a size to allow gas to pass there through to said chamber
9. A device as claimed in claim 1 wherein said catalyst poison filter is made of activated carbon.

10. A device as claimed in claim 1 wherein said poison filter comprises potassium carbonate.
11. A device as claimed in claim 9 wherein said activated carbon is impregnated with potassium carbonate.
12. A device as claimed in claim 10 wherein said activated cariDon is impregnated with potassium carbonate.
13. A device as claimed in claim 1 comprising a pressure relief vent.
14. A device as claimed in claim 1 wherein said container is made of a plastic material and is attached to a flange capable of attaching to a pressure relief vent.
15. A device for combining gases in a storage battery; comprising:
a catalyst container having an internal chamber and an opening to said chamber, said container being substantially non-porous;
a catalyst arranged within said chamber, said cataly^ capable of reacting oxygen gas and hydrogen gas;
characterized in that the said device include
a catalyst poison filter an-anged witJiln said chamba-; and
a micro-porous hydrophobic member arranged to seal said opening, said micro-porous member having por^ of suitable size to permit gas to pass there through while being a barrier to liquids.
16. A device for combining gases as claimed in claim 15 wherein said filter is arranged between said catalyst and said micro-porous member.
17. A device for combining gases as claimed claim 16 wherein said container is made of a plastic material.
18. A device for combining gases as claimed in claim 15 wherein said miao-porous member comprises a plastic material.
19. A device for combining gases as claimed in claim 15 wherein said container is cylindrical, has no more than one said opening, and comprises a plastic material, and wherein said micro-porous member comprises a plastic material.
20. A device for combining gases as claimed in claim 15 comprising a pressure relief vent, said container being attachaJ to said pressure rei\df vent.

21. A device for combining gases as claimed in claim 15 wherein said container is made of a plastic material and is attached to a flange capable of attaching to a pressure relief vent.
22. A device for combining gases as claimed in claim 20 wherein said container is supported in a holder attached to said vent.
23. A device for combing gases as claim«l in claim 15 comprising at least one tab extending from said container, said tab capable of engaging a complementary recess for holding said housing in place when installed in said storage battery.
24. A device for combining gases as claimed in claim 20 wherein said housing is snap connected to said vent cap.
25. A value regulated lead acid (VRLA) battery cell comprising:
a sealed housing;
a positive electrode positioned in the housing;
a negative electrode positioned in the housing in spaced relationship from the positive electrode;
and electrolyte in said housing in contact with said positive and negative electrodes;
a gas space within said housing in which oxygen and hydrogen gas collects;
a pressure relief vent which allows gas to escape from the housing and which prevents oxygen gas ftx)m outside the housing to contact said negative electrode;
a catalyst device an-anged to be in contact with at least a portion of said oxygen and hydrogen gas, said device including a container having a container wall and defining an internal chamber, and a catalyst arranged within said chamber, said catalyst capable of reacting oxygen gas and hydrogen gas to form water vapour; characterized in that said battery cell includes
a catalyst poison filter arrangol to be in contact with at least a portion of said oxygen and hydrogen gas.
26. A VRLA battery cell as claimed in claim 25 wherein said catalyst device
comprises a micro-porous section arranged to and having pores sized to allow oxygen
gas and hydrogen gas to pass from said gas space to said chamber, said micro-

porous section being hydrophobic to said electrolyte.
27. A VRLA battery cell as claimed in daim 26 wheran said poison filter is arranged within said chamber, and said micro-porous hydrophobic section comprises a single piece of plastic material.
28. A catalyst container for use in battery cells having an electrolyte characterized in that said container including:
a container wall comprising a plastic material;
a chamber within said container capable of holding catalyst; and
a flange attached to said container.
29. A container as claimed in claim 28 whaein said container wall has pores of
sufiRcient size to allow gas to pass through to sakj chamber, and is hydrophobic to said
electrolyte.
30. A container as claimed in claim 28 wha'ein said container wall is
impermeable to gas and liquids, and furttier includes an opening into said chamber, said
opening being sealed with a micro-porous hydrophobic member having pores of
sufficient size to allow gas to pass through to said chamber.
31. In a method for float charging a valve-regulated, lead-acid (VRLA) cell (60)
at a charge voltage, which has a value that is slightly in esccess of the value of the open
circuit voltage of ttie cell;
said cell (60) including, in spaced-apart relationship, a positive electrode (64) and a negative electrode (66) electrolyte in contact with said positive and negative electrodes (64, 66), and a catalyst (26) for combining oxygen and hydrogen gases to fonn water vapor;
wherein during charging of the cell, there is (a) a self-discharge reaction at the negative electrode (64), (b) the production at the positive and negative electrodes (64, 66) respectively of oxygen and hydrogen gases, and (c) the exothermic conversion by said catalyst of a portion of the oxygen and hydrogen gases to water;
the improvemait comprising reducing the rate at which said oxygen and hydrogen gases that are produced contact said catalyst (26) to reduce the rate at which heat is generated by said exothermic conversion of said gases to water.

32. The method as claimed in claim 31, comprises the step of filtering said gases
to remove any catalyst poisons before said gases contact said catalyst (26).
33. A device (10) for combining gas^ within a storage battery (60); comprising:
a catalyst container (14) having a container wall (18) and defining an Internal
chamber (22);
a catalyst (26) arranged within said chamber (22), said catalyst (26) capable of reacting oxygen gas and hydrogen gas to form water vapor; and
a micro-porous section (30) having por^ through which said oxygen gas and hydrogen gas can pass into said internal chamber (22) from outside of said container (14); wherein at least one of the pore size, planar surface area and thickness of said micro-porous member (30) is selected to control the amount or rate at which said oxygen and hydrogen gases can pass into said internal diamber (22) to control the heat generated by the catalytic combination of said oxygen and hydrogen gases.
34. A device as claimed in claim 33 wherein said micro-porous section (30) is arranged in at least a portion of said container wall (18).
35. A device as claimed in claim 33 wherein said container (14) comprises a plastics material.
36. A device as claimed in claim 33 wherein said micro-porous section (30) has pores ranging in size between 1 and 40 microns.
37. A device as claimed in claim 33 wherein said container (14) is substantially non-porous and has an opening (20) to said chamber, and wherein said micro-porous section (30) comprises a micro-porous hydrc^oblc member arranged to seal said opening and having pores of a size to allow gas to pass there through to said chamber (22).
38. A device as claimed in claim 33 flirther comprising a pressure relief vent (12).

39. A device as claimed in claim 33 wherein said container (14) is made of a plastic material and is attached to a flange (16) capable of attaching to a pressure relief vent.

Documents:

in-pct-2001-0949-che abstract.jpg

in-pct-2001-0949-che abstract.pdf

in-pct-2001-0949-che claims duplicate.pdf

in-pct-2001-0949-che claims.pdf

in-pct-2001-0949-che correspondence-others.pdf

in-pct-2001-0949-che correspondence-po.pdf

in-pct-2001-0949-che description (complete) duplicate.pdf

in-pct-2001-0949-che description (complete).pdf

in-pct-2001-0949-che drawings duplicate.pdf

in-pct-2001-0949-che drawings.pdf

in-pct-2001-0949-che form-1.pdf

in-pct-2001-0949-che form-19.pdf

in-pct-2001-0949-che form-26.pdf

in-pct-2001-0949-che form-3.pdf

in-pct-2001-0949-che form-5.pdf

in-pct-2001-0949-che pct.pdf

in-pct-2001-0949-che petition.pdf

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Patent Number

225845

Indian Patent Application Number

IN/PCT/2001/949/CHE

PG Journal Number

02/2009

Publication Date

09-Jan-2009

Grant Date

01-Dec-2008

Date of Filing

06-Jul-2001

Name of Patentee

JONES WILLIAM E M

Applicant Address

#A6 WATERS EDGE, OCEAN HILL BOULEVARD, FREEPORT,

Inventors:

#	Inventor's Name	Inventor's Address
1	CLAPPER JOSHUA E	1381 HALL ROAD, WEST CHESTER, PA 19380,
2	VANASSE HAROLD A	803 IRENE DRIVE, WEST CHESTER, PA 19380,

PCT International Classification Number

HO1M10/52

PCT International Application Number

PCT/US99/29793

PCT International Filing date

1999-12-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/148,536	1999-08-12	U.S.A.
2	60/112,305	1998-12-14	U.S.A.
3	60/113,579	1998-12-24	U.S.A.