US20080087868A1 - Battery paste material and method - Google Patents
Battery paste material and method Download PDFInfo
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- US20080087868A1 US20080087868A1 US11/907,133 US90713307A US2008087868A1 US 20080087868 A1 US20080087868 A1 US 20080087868A1 US 90713307 A US90713307 A US 90713307A US 2008087868 A1 US2008087868 A1 US 2008087868A1
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- lead sulfate
- paste
- tetrabasic lead
- battery
- tetrabasic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
- H01M4/21—Drying of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Definitions
- the present invention relates generally to the field of batteries (e.g., lead-acid batteries such as automotive starting, lighting, and ignition (SLI) batteries; industrial batteries; commercial batteries; and marine batteries). More specifically, the present invention relates to materials for use in active materials for batteries and methods of making such materials.
- batteries e.g., lead-acid batteries such as automotive starting, lighting, and ignition (SLI) batteries; industrial batteries; commercial batteries; and marine batteries.
- Positive and negative plates or grids utilized in lead-acid batteries are made of lead or a lead alloy, and include a plurality of wires coupled to a plurality of nodes (e.g., a battery plate may include a frame comprising four sides with a lug or current collector extending from one of the sides and a network of wires or grid elements interconnected with a plurality of nodes).
- a battery plate may include a frame comprising four sides with a lug or current collector extending from one of the sides and a network of wires or grid elements interconnected with a plurality of nodes).
- the positive grids or plates have a material (e.g., a paste) applied thereto.
- the paste typically comprises lead oxide (PbO).
- the active material may also include one or both of tetrabasic lead sulfate (4PbO.PbSO 4 ) (often abbreviated as “4BS”) and tribasic lead sulfate (3PbO.PbSO 4 .H2O) (often abbreviated as “3BS”).
- 4BS tetrabasic lead sulfate
- 3PbO.PbSO 4 .H2O tribasic lead sulfate
- an active material may comprise approximately 40% PbO and 60% 4BS.
- the active material may have a different composition (e.g., the active material may include between approximately 10% and 100% 4BS, etc.).
- tetrabasic lead sulfate and tribasic lead sulfate may be provided in the form of individual crystals that are mixed into the lead oxide paste material.
- tetrabasic lead sulfate and tribasic lead sulfate may be provided by adding acid to a paste mix under appropriate mixing and plate curing conditions.
- the positive plates having paste applied thereto are cured or dried to remove excess liquid in the paste and assembled into a battery (e.g., positive and negative plates are provided with a separator between them in a battery container, after which acid (e.g., sulfuric acid) is introduced into the battery).
- acid e.g., sulfuric acid
- the tetrabasic lead sulfate and/or tribasic lead sulfate crystals grow or increase in size.
- the components of the paste are converted to an active material such as lead dioxide (PbO 2 ) on the positive plates and sponge lead (Pb) on the negative plates.
- PbO 2 lead dioxide
- Pb sponge lead
- a sulfation reaction proceeds as acid is added to the battery according to the formula: PbO+H 2 SO 4 ⁇ PbSO 4 +H 2 O
- the reactions at the positive and negative plates proceed according to the following formulae:
- Cured positive plates containing tetrabasic lead sulfate as a component of the paste applied thereto may provide improved deep discharge cycle life as compared to cured positive plates utilizing tribasic lead sulfate as a component in the paste.
- B. Culpin has provided a review of 4BS positive plate chemistry and its benefits in J. Power Sources, 25, p. 305-311 (1989).
- Another potential advantageous feature is that improved discharge capacity of positive plates utilizing tetrabasic lead sulfate may be obtained as compared to plates utilizing tribasic lead sulfate.
- batteries produced using tetrabasic lead sulfate positive plate technology have been shown to yield up to approximately 20% improvements in reserve capacity (where reserve capacity is defined as the number of minutes at a 25 ampere discharge at 80° F. until a battery voltage is reduced to 10.5 volts).
- Tetrabasic lead sulfate is conventionally provided having a crystal thickness of between approximately 10 and 20 micrometers and a length of between approximately 60 and 90 micrometers.
- One difficulty with using such tetrabasic lead sulfate is that the crystal size may not be optimum for allowing conversion of the paste materials into lead dioxide during the formation process.
- Another difficulty is that the use of such tetrabasic lead sulfate requires that the positive plates undergo a high temperature steam cure for approximately 1 hour or more.
- Another difficulty in utilizing tetrabasic lead sulfate chemistry is that the paste mixing process and/or the plate curing step must be performed at elevated temperatures of at least 70° C. and more typically exceeding 80° C. Such elevated temperatures may not desirable for such manufacturing processes, and may result in increased manufacturing cost and decreased manufacturing efficiency.
- the present invention relates to a method of making a battery plate that includes mixing particles of tetrabasic lead sulfate with leady oxide to form a paste material.
- the particles have an average spherical particle diameter of less than approximately 2.5 micrometers.
- the method also includes providing at least a portion of the paste material on a battery grid curing the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to produce a battery plate having a cured paste thereon.
- the present invention also relates to a method of making a plate for a battery that includes mixing particles of tetrabasic lead sulfate having an average spherical particle diameter of less than approximately 2 micrometers with leady oxide to form a paste.
- the method also includes coating at least a portion of a battery grid with the paste and heating the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to produce a battery plate having a cured paste thereon.
- the present invention also relates to a method of making a battery that includes adding tetrabasic lead sulfate particles having an average spherical particle diameter of less than approximately 2.5 micrometers to leady oxide to form a paste material.
- the method also includes providing at least a portion of the paste material on a battery grid and curing the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to form a battery plate having a cured paste thereon.
- the method also includes providing the battery plate in a container to produce a battery and charging the battery.
- FIG. 1 shows a 2000 ⁇ magnification scanning electron micrograph of a conventional positive plate utilizing a tribasic lead sulfate chemistry (i.e., without the use of tetrabasic lead sulfate) which had been cured at a low temperature of 46° C. for 16 hrs at 95% humidity.
- FIG. 2 shows a 2000 ⁇ magnification scanning electron micrograph of a positive plate which had been cured under the same low temperature conditions as for the plate shown in FIG. 1 , but which utilized a paste mix with 1 wt % of a tetrabasic lead sulfate seed crystal additive.
- FIG. 3 shows a 2000 ⁇ magnification scanning electron micrograph of a positive plate having larger sized tetrabasic lead sulfate crystals which was made using high temperature curing (approximately 100° C.) without the benefit of a tetrabasic lead sulfate seed crystal additive.
- FIG. 4 is a graph illustrating a theoretical quantitative prediction of percent tetrabasic lead sulfate conversion in low temperature cured plates versus seed crystal spherical diameter.
- a process or method of manufacturing positive plates or grids utilizing tetrabasic lead sulfate as a component of the battery paste provides a savings in positive plate materials (e.g., between 4 and 8%), with little or no loss in lead acid battery performance or cycle life and little or no decline in manufacturing productivity.
- the process allows paste mixing temperatures of less than 60° C. and curing temperatures of less than 46° C. to be utilized. Such temperatures are significantly lower than temperatures used for conventional tetrabasic lead sulfate plate chemistry manufacturing processes, which may range from approximately 70° to 80° or higher.
- finely ground or milled tetrabasic lead sulfate particles at a loading level of approximately 1 wt % are added to leady oxide in an otherwise standard paste mixing process.
- the particles have an average spherical particle diameter of less than approximately 2.5 micrometers ( ⁇ m) (i.e., the particles are generally spherical and have a particle diameter of less than approximately 2.5 micrometers).
- the particles have an average spherical particle diameter of up to approximately 2 micrometers.
- the particles have an average spherical particle diameter of approximately 1 micrometer.
- the particles have an average spherical particle diameter of approximately 2 micrometers. According to an exemplary embodiment, the particles have an average spherical particle diameter of between approximately 1 and 2 micrometers. According to other exemplary embodiments, the particles may have a different average spherical particle diameter (e.g., 2 micrometers or greater).
- the particles will grow through nucleation and grain growth to sizes smaller than would be possible using conventional high temperature curing (e.g., between approximately 2 and 5 micrometers thick (preferably approximately 3 micrometers thick) and between approximately 20 and 30 micrometers long).
- the tetrabasic lead sulfate crystals comprise between approximately 50 and 60% by weight of the cured paste.
- a higher or lower acid content in the paste may be used to obtain levels of tetrabasic lead sulfate that are between approximately 10% and 100% by weight of the cured plate.
- the total weight of tetrabasic lead sulfate may also vary based on the amount of tetrabasic lead sulfate particles utilized.
- One advantageous feature of utilizing relatively finely ground tetrabasic lead sulfate particles or “seed crystals” is that greater than approximately 90% of all PbSO 4 may be converted into tetrabasic lead sulfate. No further curing process (e.g., a steam curing process) is required. In contrast, conventional tetrabasic lead sulfate production methods may require the use of a steam curing process, which adds an additional step to the manufacturing process.
- the tetrabasic lead sulfate particles or “seed crystals” catalyze the full conversion of all tribasic lead sulfate chemistry into tetrabasic lead sulfate at a curing temperature of between approximately 46° and 48° C., provided that the humidity is maintained at approximately 95%. According to other exemplary embodiments, the humidity may be maintained at a different level (e.g., between approximately 80 and 100%).
- One advantageous feature of utilizing such temperatures is that lower manufacturing temperatures require less energy and avoid the higher costs associated with the use of warpage resistant fiber filled plastic stacking boards to hold the plates during the curing process. Further, high temperature paste mixing processes may require more expensive process equipment (e.g., vacuum-cooled paste mixers).
- each tetrabasic lead sulfate seed crystal develops into a single cured tetrabasic lead sulfate crystal.
- the greater the number of seed crystals the greater the number of cured crystals.
- the final cured crystals have a smaller size than those produced using conventional processes (e.g., the growth of each of the seed crystals into the larger, cured crystals is constrained due to the number of seed crystals provided).
- the relatively small cured crystal sizes may be produced regardless of curing temperature.
- the tetrabasic lead sulfate particles are produced by jet milling larger particles of tetrabasic lead sulfate to obtain an average spherical particle diameter of between approximately 1 and 2 micrometers.
- a Fluid Energy Aljet Model 8 Micro-Jet Grinding System manufactured by Fluid Energy Aljet of Telford, Pa.
- tetrabasic lead sulfate seed crystals or particles having reduced spherical particle diameters e.g., between approximately 1 and 2 micrometers.
- other types of jet mills or other milling or grinding equipment may be used.
- other methods of producing tetrabasic lead sulfate particles having particle sizes smaller than those conventionally used may also be utilized.
- the average tetrabasic lead sulfate spherical particle size may differ.
- the average particle size and loading levels may vary to optimize the conversion of tetrabasic lead sulfate to lead dioxide during the formation process.
- the spherical particle diameter of the tetrabasic lead sulfate particles may range between approximately 2 and 5 micrometers.
- the tetrabasic lead sulfate particles may be provided with a plurality of particle sizes (e.g., approximately 10% of the tetrabasic lead sulfate particles have average spherical particle diameters of between approximately 10 and 20 micrometers, and 90% of the tetrabasic lead sulfate particles have a spherical particle diameter of approximately 1 micrometer).
- the particular mixture of particle sizes may vary according to various considerations.
- the amount of loading of the paste with tetrabasic lead sulfate seed crystals may range between approximately 0.5% and 10.0% by weight. Other loading amounts may also be used according to other exemplary embodiments.
- tetrabasic lead sulfate particles having reduced sizes are advantageous features of the use of tetrabasic lead sulfate particles having reduced sizes.
- the tetrabasic lead sulfate crystals result in a cured tetrabasic lead sulfate crystal size that is small enough to provide relatively efficient conversion to lead dioxide positive active material in the first charge of the lead acid battery (commonly referred to as the formation process).
- FIG. 1 shows a 2000 ⁇ magnification scanning electron micrograph of a conventional positive plate utilizing a tribasic lead sulfate chemistry (i.e., without the use of tetrabasic lead sulfate) which had been cured at a low temperature of 46° C. for 16 hrs at 95% humidity.
- the small crystalline structure illustrated in the micrograph is characteristic of conventional tribasic lead sulfate chemistry, as was confirmed by x-ray diffraction and thermal gravimetric analysis (J. Materials Science Letters, Vol. 11, pp 369-372 (1992)).
- FIG. 2 shows a scanning electron micrograph at the same 2000 ⁇ magnification of a plate which had been cured under the same low temperature conditions as for the plate shown in FIG. 1 , but which utilized a paste mix with 1 wt % of a tetrabasic lead sulfate seed crystal additive.
- the use of tetrabasic lead sulfate crystals according to an exemplary embodiment provides larger 2-3 micrometer thick crystals.
- Such cured crystal size is desirable since such crystals are optimally sized to convert to lead dioxide during the battery formation process, while at the same time yielding life and performance improvements over tribasic lead sulfate plate chemistry.
- X-ray diffraction and thermal gravimetric analyses confirmed that more than 90% of the PbSO 4 present in the plate had been converted into the tetrabasic lead sulfate crystalline form.
- FIG. 3 shows a 2000 ⁇ magnification scanning electron micrograph of a plate having larger sized tetrabasic lead sulfate crystals which was made using high temperature curing (approximately 100° C.) without the benefit of a milled tetrabasic lead sulfate seed crystal additive.
- the plates were steam cured at a temperature of approximately 100° C.
- the much larger, approximately 10 micrometer thick tetrabasic lead sulfate are more difficult to convert into lead dioxide positive plate active material during subsequent battery formation processes. Such plates also show a greater tendency toward warpage during the formation process.
- tetrabasic lead sulfate “seed crystals” of nominal 1-2 micrometer spherical particle diameter provides a relatively simple and robust process which assures that the proper size and amount of tetrabasic lead sulfate seed material is in the plate during the subsequent, critical plate curing step.
- the degree of conversion of PbSO 4 into the desired tetrabasic lead sulfate chemistry is also critically controlled by tetrabasic lead sulfate seed crystal particle size at the relatively low curing temperatures which would not otherwise create more tetrabasic lead sulfate crystals during curing.
- a theoretical quantitative prediction of percent tetrabasic lead sulfate conversion in low temperature cured plates versus seed crystal diameter is shown in FIG. 4 .
- One assumption forming the basis of FIG. 4 is that low temperature cured tetrabasic lead sulfate crystals cannot grow larger than about 3 micrometers thick and 30 micrometers long.
- the number of these cured crystals determines the percent conversion to tetrabasic lead sulfate in the cured plates. Increasing the number of tetrabasic lead sulfate seed crystals per unit weight of additive via particle size reduction increases the percent conversion of tetrabasic lead sulfate in the cured plate by creating greater number of nucleation sites to create greater numbers of cured tetrabasic lead sulfate crystals.
- FIG. 4 shows that seed crystal spherical diameters need to be no larger than about 2 micrometers in diameter to assure full conversion to tetrabasic lead sulfate crystals in the curing process. Still smaller seed crystal sizes would more robustly ensure full conversion to tetrabasic lead sulfate at low curing temperatures and could enable the use of a smaller amount of seed crystal additive to reduce process costs.
- the paste material utilizing tetrabasic lead sulfate seed crystals yields improvements over conventional tetrabasic lead sulfate plate production by circumventing the need for an additional high temperature steam curing process.
- the method also generates optimally-sized post-cure tetrabasic lead sulfate crystals that are more efficiently converted to lead dioxide than possible using conventional tetrabasic lead sulfate plate production methods.
- the use of such seed crystals advantageously retains the benefits of tetrabasic lead sulfate plate chemistry such as a 5-15% increase in positive plate material utilization, improved discharge capacity stability during repetitive reserve capacity testing, and improved deep discharge cycle life.
- a method for producing or manufacturing battery plates utilizing tetrabasic lead sulfate paste chemistry in accordance with the teachings described herein may utilize lower temperatures than conventional methods. That is, low temperatures may be utilized to cure the battery paste once coated on a plate or grid.
- Relatively small seed crystals of tetrabasic lead sulfate are used according to an exemplary embodiment to produce smaller crystals of tetrabasic lead sulfate after a curing operation than possible using conventional methods, while exhibiting a higher percentage of tetrabasic lead sulfate conversion to lead dioxide during a battery formation process than may be obtained using conventional manufacturing methods.
- Such a process may provide a relatively simple, robust, and cost effective means for making cured lead acid battery plates with relatively high percent conversion to optimally sized (2-5 micrometer thick) tetrabasic lead sulfate, which in turn can be relatively efficiently converted into lead dioxide active material during the battery formation process.
- active material paste weights may be reduced without degrading battery performance or cycle life and without significantly increasing manufacturing costs or decreasing manufacturing efficiency.
- Tribasic lead sulfate contaminant Greater than 90 wt % purity tetrabasic lead sulfate (tribasic lead sulfate contaminant) was prepared in 60 lb lots in 50 gallons of hot aqueous slurries according to a procedure described by Biagetti and Weeks in the September 1970 issue of the Bell System Technical Journal. The dried material was jet milled to average volume based spherical particle diameters of 1 micrometer with a nominal standard deviation of 1 micrometers. Laser based particle size analyzers were used to quantitate all tetrabasic lead sulfate seed particle sizes.
- the tetrabasic lead sulfate seed particles were added to a 2400 lb paste mix of conventional leady oxide to achieve a desired 1 wt % loading level (i.e., 24 lbs. of lead sulfate seeds were added to the mix). Normal state of the art mixing was then conducted via water additions, followed by the appropriate amount of 1.325 specific gravity sulfuric acid addition over a nominal 10 minute period to yield nominal peak mix temperatures of 60° C.
- Machine pasted plates were then flash dried to a nominal moisture content of 10% and then subjected to 16 hours of curing at 46° C. and 95% humidity. The plates were then dried for a nominal 30 hours at 60° C. at low humidities not to exceed 50%. Conventional battery assembly and formations followed to make test batteries. Battery Council International (BCI) testing procedures and equipment were used to conduct performance and life testing of all batteries.
- BCI Battery Council International
Abstract
A method of making a battery plate includes mixing particles of tetrabasic lead sulfate with leady oxide to form a paste material. The particles having an average spherical particle diameter of less than approximately 2.5 micrometers. The method also includes providing at least a portion of the paste material on a battery grid curing the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to produce a battery plate having a cured paste thereon.
Description
- The present application is a continuation of U.S. patent application Ser. No. 10/576,427 and also claims the benefit of and priority to the following applications: International Patent Application No. PCT/US2004/034710 filed Oct. 21, 2004 and U.S. Provisional Patent Application No. 60/512,951, filed Oct. 21, 2003. The aforementioned patent applications are hereby incorporated by reference in their entireties.
- The present invention relates generally to the field of batteries (e.g., lead-acid batteries such as automotive starting, lighting, and ignition (SLI) batteries; industrial batteries; commercial batteries; and marine batteries). More specifically, the present invention relates to materials for use in active materials for batteries and methods of making such materials.
- Positive and negative plates or grids utilized in lead-acid batteries are made of lead or a lead alloy, and include a plurality of wires coupled to a plurality of nodes (e.g., a battery plate may include a frame comprising four sides with a lug or current collector extending from one of the sides and a network of wires or grid elements interconnected with a plurality of nodes).
- At least a portion of the positive grids or plates have a material (e.g., a paste) applied thereto. The paste typically comprises lead oxide (PbO). The active material may also include one or both of tetrabasic lead sulfate (4PbO.PbSO4) (often abbreviated as “4BS”) and tribasic lead sulfate (3PbO.PbSO4.H2O) (often abbreviated as “3BS”). According to an exemplary embodiment, an active material may comprise approximately 40% PbO and 60% 4BS. According to other exemplary embodiments, the active material may have a different composition (e.g., the active material may include between approximately 10% and 100% 4BS, etc.). The tetrabasic lead sulfate and tribasic lead sulfate may be provided in the form of individual crystals that are mixed into the lead oxide paste material. According to an exemplary embodiment, tetrabasic lead sulfate and tribasic lead sulfate may be provided by adding acid to a paste mix under appropriate mixing and plate curing conditions.
- The positive plates having paste applied thereto are cured or dried to remove excess liquid in the paste and assembled into a battery (e.g., positive and negative plates are provided with a separator between them in a battery container, after which acid (e.g., sulfuric acid) is introduced into the battery). During curing, the tetrabasic lead sulfate and/or tribasic lead sulfate crystals grow or increase in size.
- During battery formation (e.g., providing an initial charge to the battery), the components of the paste are converted to an active material such as lead dioxide (PbO2) on the positive plates and sponge lead (Pb) on the negative plates. According to an exemplary embodiment, a sulfation reaction proceeds as acid is added to the battery according to the formula:
PbO+H2SO4═PbSO4+H2O - During formation, according to an exemplary embodiment, the reactions at the positive and negative plates proceed according to the following formulae:
-
PbSO4+2H2O═PbO2+H2SO4+2H++2e−
PbO+H2O═PbO2+2H++2e− -
PbSO4+2H++2e−=Pb+H2SO4
PbO+2H++2e−=Pb+H2O -
2PbSO4+2H2O═PbO2+Pb+2H2SO4
2PbO═PbO2+Pb - Cured positive plates containing tetrabasic lead sulfate as a component of the paste applied thereto may provide improved deep discharge cycle life as compared to cured positive plates utilizing tribasic lead sulfate as a component in the paste. B. Culpin has provided a review of 4BS positive plate chemistry and its benefits in J. Power Sources, 25, p. 305-311 (1989).
- Another potential advantageous feature is that improved discharge capacity of positive plates utilizing tetrabasic lead sulfate may be obtained as compared to plates utilizing tribasic lead sulfate. For example, batteries produced using tetrabasic lead sulfate positive plate technology have been shown to yield up to approximately 20% improvements in reserve capacity (where reserve capacity is defined as the number of minutes at a 25 ampere discharge at 80° F. until a battery voltage is reduced to 10.5 volts).
- Tetrabasic lead sulfate is conventionally provided having a crystal thickness of between approximately 10 and 20 micrometers and a length of between approximately 60 and 90 micrometers. One difficulty with using such tetrabasic lead sulfate is that the crystal size may not be optimum for allowing conversion of the paste materials into lead dioxide during the formation process. Another difficulty is that the use of such tetrabasic lead sulfate requires that the positive plates undergo a high temperature steam cure for approximately 1 hour or more.
- One detrimental effect of the use of conventional tetrabasic lead sulfate crystals is that plates utilizing such crystals may exhibit incomplete formation (i.e., not all tetrabasic lead sulfate is converted to lead dioxide active material during initial charging). Accordingly, batteries produced with such plates may require follow-up boost charging to complete the formation process. The large crystals, coupled with incomplete formation, also may result in warpage of the formed positive plates.
- Another difficulty in utilizing tetrabasic lead sulfate chemistry is that the paste mixing process and/or the plate curing step must be performed at elevated temperatures of at least 70° C. and more typically exceeding 80° C. Such elevated temperatures may not desirable for such manufacturing processes, and may result in increased manufacturing cost and decreased manufacturing efficiency.
- There is thus a need to provide an improved method for producing tetrabasic lead sulfate materials for use in battery paste. There is also a need to provide a battery paste having tetrabasic lead sulfate with an optimum crystal size to enable relatively efficient conversion of the tetrabasic lead sulfate into lead dioxide active material. There is further a need to provide a relatively efficient and cost-effective method of producing battery paste for use in lead-acid batteries. There is further a need to provide a method for producing materials for use in battery paste that decrease the material requirements for production of a battery without sacrificing battery performance or cycle life and without reducing manufacturing efficiency. These and other needs may be met by one or more of the exemplary embodiments described herein.
- The present invention relates to a method of making a battery plate that includes mixing particles of tetrabasic lead sulfate with leady oxide to form a paste material. The particles have an average spherical particle diameter of less than approximately 2.5 micrometers. The method also includes providing at least a portion of the paste material on a battery grid curing the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to produce a battery plate having a cured paste thereon.
- The present invention also relates to a method of making a plate for a battery that includes mixing particles of tetrabasic lead sulfate having an average spherical particle diameter of less than approximately 2 micrometers with leady oxide to form a paste. The method also includes coating at least a portion of a battery grid with the paste and heating the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to produce a battery plate having a cured paste thereon.
- The present invention also relates to a method of making a battery that includes adding tetrabasic lead sulfate particles having an average spherical particle diameter of less than approximately 2.5 micrometers to leady oxide to form a paste material. The method also includes providing at least a portion of the paste material on a battery grid and curing the battery grid and paste material at a temperature of less than approximately 48 degrees Celsius to form a battery plate having a cured paste thereon. The method also includes providing the battery plate in a container to produce a battery and charging the battery.
-
FIG. 1 shows a 2000× magnification scanning electron micrograph of a conventional positive plate utilizing a tribasic lead sulfate chemistry (i.e., without the use of tetrabasic lead sulfate) which had been cured at a low temperature of 46° C. for 16 hrs at 95% humidity. -
FIG. 2 shows a 2000× magnification scanning electron micrograph of a positive plate which had been cured under the same low temperature conditions as for the plate shown inFIG. 1 , but which utilized a paste mix with 1 wt % of a tetrabasic lead sulfate seed crystal additive. -
FIG. 3 shows a 2000× magnification scanning electron micrograph of a positive plate having larger sized tetrabasic lead sulfate crystals which was made using high temperature curing (approximately 100° C.) without the benefit of a tetrabasic lead sulfate seed crystal additive. -
FIG. 4 is a graph illustrating a theoretical quantitative prediction of percent tetrabasic lead sulfate conversion in low temperature cured plates versus seed crystal spherical diameter. - According to an exemplary embodiment, a process or method of manufacturing positive plates or grids utilizing tetrabasic lead sulfate as a component of the battery paste (e.g., along with PbO) provides a savings in positive plate materials (e.g., between 4 and 8%), with little or no loss in lead acid battery performance or cycle life and little or no decline in manufacturing productivity.
- According to an exemplary embodiment, the process allows paste mixing temperatures of less than 60° C. and curing temperatures of less than 46° C. to be utilized. Such temperatures are significantly lower than temperatures used for conventional tetrabasic lead sulfate plate chemistry manufacturing processes, which may range from approximately 70° to 80° or higher.
- According to an exemplary embodiment, finely ground or milled tetrabasic lead sulfate particles at a loading level of approximately 1 wt % are added to leady oxide in an otherwise standard paste mixing process. According to an exemplary embodiment, the particles have an average spherical particle diameter of less than approximately 2.5 micrometers (μm) (i.e., the particles are generally spherical and have a particle diameter of less than approximately 2.5 micrometers). According to an exemplary embodiment, the particles have an average spherical particle diameter of up to approximately 2 micrometers. According to an exemplary embodiment, the particles have an average spherical particle diameter of approximately 1 micrometer. According to an exemplary embodiment, the particles have an average spherical particle diameter of approximately 2 micrometers. According to an exemplary embodiment, the particles have an average spherical particle diameter of between approximately 1 and 2 micrometers. According to other exemplary embodiments, the particles may have a different average spherical particle diameter (e.g., 2 micrometers or greater).
- Following curing of the battery paste at a relatively low temperature, the particles will grow through nucleation and grain growth to sizes smaller than would be possible using conventional high temperature curing (e.g., between approximately 2 and 5 micrometers thick (preferably approximately 3 micrometers thick) and between approximately 20 and 30 micrometers long). Following the curing step, which causes growth of the tetrabasic lead sulfate crystals, the tetrabasic lead sulfate crystals comprise between approximately 50 and 60% by weight of the cured paste. According to other exemplary embodiments, a higher or lower acid content in the paste may be used to obtain levels of tetrabasic lead sulfate that are between approximately 10% and 100% by weight of the cured plate. According to still other exemplary embodiments, the total weight of tetrabasic lead sulfate may also vary based on the amount of tetrabasic lead sulfate particles utilized.
- One advantageous feature of utilizing relatively finely ground tetrabasic lead sulfate particles or “seed crystals” is that greater than approximately 90% of all PbSO4 may be converted into tetrabasic lead sulfate. No further curing process (e.g., a steam curing process) is required. In contrast, conventional tetrabasic lead sulfate production methods may require the use of a steam curing process, which adds an additional step to the manufacturing process.
- The tetrabasic lead sulfate particles or “seed crystals” catalyze the full conversion of all tribasic lead sulfate chemistry into tetrabasic lead sulfate at a curing temperature of between approximately 46° and 48° C., provided that the humidity is maintained at approximately 95%. According to other exemplary embodiments, the humidity may be maintained at a different level (e.g., between approximately 80 and 100%). One advantageous feature of utilizing such temperatures is that lower manufacturing temperatures require less energy and avoid the higher costs associated with the use of warpage resistant fiber filled plastic stacking boards to hold the plates during the curing process. Further, high temperature paste mixing processes may require more expensive process equipment (e.g., vacuum-cooled paste mixers).
- One advantageous feature of using small tetrabasic lead sulfate seed crystals is that the required amount of tetrabasic lead sulfate is reduced, which thus reduces the cost of this paste mix additive. According to an exemplary embodiment, each tetrabasic lead sulfate seed crystal develops into a single cured tetrabasic lead sulfate crystal. The greater the number of seed crystals, the greater the number of cured crystals. Because there are a greater number of seed crystals, the final cured crystals have a smaller size than those produced using conventional processes (e.g., the growth of each of the seed crystals into the larger, cured crystals is constrained due to the number of seed crystals provided). The relatively small cured crystal sizes may be produced regardless of curing temperature.
- The tetrabasic lead sulfate particles are produced by jet milling larger particles of tetrabasic lead sulfate to obtain an average spherical particle diameter of between approximately 1 and 2 micrometers. According to an exemplary embodiment, a Fluid Energy Aljet Model 8 Micro-Jet Grinding System (manufactured by Fluid Energy Aljet of Telford, Pa.) may be utilized to produce tetrabasic lead sulfate seed crystals or particles having reduced spherical particle diameters (e.g., between approximately 1 and 2 micrometers). According to other exemplary embodiments, other types of jet mills or other milling or grinding equipment may be used. According to other exemplary embodiments, other methods of producing tetrabasic lead sulfate particles having particle sizes smaller than those conventionally used may also be utilized.
- According to other exemplary embodiments, the average tetrabasic lead sulfate spherical particle size may differ. For example, the average particle size and loading levels may vary to optimize the conversion of tetrabasic lead sulfate to lead dioxide during the formation process. According to one embodiment, the spherical particle diameter of the tetrabasic lead sulfate particles may range between approximately 2 and 5 micrometers. According to another exemplary embodiment, the tetrabasic lead sulfate particles may be provided with a plurality of particle sizes (e.g., approximately 10% of the tetrabasic lead sulfate particles have average spherical particle diameters of between approximately 10 and 20 micrometers, and 90% of the tetrabasic lead sulfate particles have a spherical particle diameter of approximately 1 micrometer). The particular mixture of particle sizes may vary according to various considerations. According to another exemplary embodiment, the amount of loading of the paste with tetrabasic lead sulfate seed crystals may range between approximately 0.5% and 10.0% by weight. Other loading amounts may also be used according to other exemplary embodiments.
- One advantageous feature of the use of tetrabasic lead sulfate particles having reduced sizes is that the tetrabasic lead sulfate crystals result in a cured tetrabasic lead sulfate crystal size that is small enough to provide relatively efficient conversion to lead dioxide positive active material in the first charge of the lead acid battery (commonly referred to as the formation process).
-
FIG. 1 shows a 2000× magnification scanning electron micrograph of a conventional positive plate utilizing a tribasic lead sulfate chemistry (i.e., without the use of tetrabasic lead sulfate) which had been cured at a low temperature of 46° C. for 16 hrs at 95% humidity. The small crystalline structure illustrated in the micrograph is characteristic of conventional tribasic lead sulfate chemistry, as was confirmed by x-ray diffraction and thermal gravimetric analysis (J. Materials Science Letters, Vol. 11, pp 369-372 (1992)). - In contrast,
FIG. 2 shows a scanning electron micrograph at the same 2000× magnification of a plate which had been cured under the same low temperature conditions as for the plate shown inFIG. 1 , but which utilized a paste mix with 1 wt % of a tetrabasic lead sulfate seed crystal additive. The use of tetrabasic lead sulfate crystals according to an exemplary embodiment provides larger 2-3 micrometer thick crystals. Such cured crystal size is desirable since such crystals are optimally sized to convert to lead dioxide during the battery formation process, while at the same time yielding life and performance improvements over tribasic lead sulfate plate chemistry. X-ray diffraction and thermal gravimetric analyses confirmed that more than 90% of the PbSO4 present in the plate had been converted into the tetrabasic lead sulfate crystalline form. -
FIG. 3 shows a 2000× magnification scanning electron micrograph of a plate having larger sized tetrabasic lead sulfate crystals which was made using high temperature curing (approximately 100° C.) without the benefit of a milled tetrabasic lead sulfate seed crystal additive. The plates were steam cured at a temperature of approximately 100° C. The much larger, approximately 10 micrometer thick tetrabasic lead sulfate are more difficult to convert into lead dioxide positive plate active material during subsequent battery formation processes. Such plates also show a greater tendency toward warpage during the formation process. - Use of tetrabasic lead sulfate “seed crystals” of nominal 1-2 micrometer spherical particle diameter provides a relatively simple and robust process which assures that the proper size and amount of tetrabasic lead sulfate seed material is in the plate during the subsequent, critical plate curing step.
- The degree of conversion of PbSO4 into the desired tetrabasic lead sulfate chemistry is also critically controlled by tetrabasic lead sulfate seed crystal particle size at the relatively low curing temperatures which would not otherwise create more tetrabasic lead sulfate crystals during curing. A theoretical quantitative prediction of percent tetrabasic lead sulfate conversion in low temperature cured plates versus seed crystal diameter is shown in
FIG. 4 . One assumption forming the basis ofFIG. 4 is that low temperature cured tetrabasic lead sulfate crystals cannot grow larger than about 3 micrometers thick and 30 micrometers long. The number of these cured crystals determines the percent conversion to tetrabasic lead sulfate in the cured plates. Increasing the number of tetrabasic lead sulfate seed crystals per unit weight of additive via particle size reduction increases the percent conversion of tetrabasic lead sulfate in the cured plate by creating greater number of nucleation sites to create greater numbers of cured tetrabasic lead sulfate crystals. -
FIG. 4 shows that seed crystal spherical diameters need to be no larger than about 2 micrometers in diameter to assure full conversion to tetrabasic lead sulfate crystals in the curing process. Still smaller seed crystal sizes would more robustly ensure full conversion to tetrabasic lead sulfate at low curing temperatures and could enable the use of a smaller amount of seed crystal additive to reduce process costs. - The paste material utilizing tetrabasic lead sulfate seed crystals yields improvements over conventional tetrabasic lead sulfate plate production by circumventing the need for an additional high temperature steam curing process. The method also generates optimally-sized post-cure tetrabasic lead sulfate crystals that are more efficiently converted to lead dioxide than possible using conventional tetrabasic lead sulfate plate production methods. The use of such seed crystals advantageously retains the benefits of tetrabasic lead sulfate plate chemistry such as a 5-15% increase in positive plate material utilization, improved discharge capacity stability during repetitive reserve capacity testing, and improved deep discharge cycle life.
- Various advantageous features may be realized utilizing the teachings of the present application. For example, a method for producing or manufacturing battery plates utilizing tetrabasic lead sulfate paste chemistry in accordance with the teachings described herein may utilize lower temperatures than conventional methods. That is, low temperatures may be utilized to cure the battery paste once coated on a plate or grid.
- Relatively small seed crystals of tetrabasic lead sulfate are used according to an exemplary embodiment to produce smaller crystals of tetrabasic lead sulfate after a curing operation than possible using conventional methods, while exhibiting a higher percentage of tetrabasic lead sulfate conversion to lead dioxide during a battery formation process than may be obtained using conventional manufacturing methods. Such a process may provide a relatively simple, robust, and cost effective means for making cured lead acid battery plates with relatively high percent conversion to optimally sized (2-5 micrometer thick) tetrabasic lead sulfate, which in turn can be relatively efficiently converted into lead dioxide active material during the battery formation process.
- Other advantages may also be obtained. For example, active material paste weights may be reduced without degrading battery performance or cycle life and without significantly increasing manufacturing costs or decreasing manufacturing efficiency.
- The following nonexclusive example illustrates features of the present invention:
- Greater than 90 wt % purity tetrabasic lead sulfate (tribasic lead sulfate contaminant) was prepared in 60 lb lots in 50 gallons of hot aqueous slurries according to a procedure described by Biagetti and Weeks in the September 1970 issue of the Bell System Technical Journal. The dried material was jet milled to average volume based spherical particle diameters of 1 micrometer with a nominal standard deviation of 1 micrometers. Laser based particle size analyzers were used to quantitate all tetrabasic lead sulfate seed particle sizes.
- The tetrabasic lead sulfate seed particles were added to a 2400 lb paste mix of conventional leady oxide to achieve a desired 1 wt % loading level (i.e., 24 lbs. of lead sulfate seeds were added to the mix). Normal state of the art mixing was then conducted via water additions, followed by the appropriate amount of 1.325 specific gravity sulfuric acid addition over a nominal 10 minute period to yield nominal peak mix temperatures of 60° C.
- Machine pasted plates were then flash dried to a nominal moisture content of 10% and then subjected to 16 hours of curing at 46° C. and 95% humidity. The plates were then dried for a nominal 30 hours at 60° C. at low humidities not to exceed 50%. Conventional battery assembly and formations followed to make test batteries. Battery Council International (BCI) testing procedures and equipment were used to conduct performance and life testing of all batteries.
- X-ray diffraction was used to confirm all tribasic lead sulfate and tetrabasic lead sulfate cured plate chemistries, while thermal gravimetric analysis was coupled with chemical sulfate analyses to quantitate these species according to the procedure described in the Journal of Material Sciences Letters, Vol 11, pp 369-372 (1992).
- It is important to note that the various exemplary embodiments are illustrative only. Although only a few embodiments of the present inventions have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, etc.) without materially departing from the novel teachings and advantages of the subject matter recited herein. Other substitutions, modifications, changes and omissions may be made in the design, process parameters, material properties, operating conditions and other features of the preferred and other exemplary embodiments without departing from the scope of the present invention.
Claims (25)
1. A method of making a battery plate paste comprising the steps of:
mixing together water and lead oxide;
mixing sulfuric acid into the water and lead oxide mixture; and
reacting the mixture of water, lead oxide and sulfuric acid in the presence of tetrabasic lead sulfate seed crystals to thereby form a paste material containing tetrabasic lead sulfate crystals.
2. The method of claim 1 , further comprising the step of reducing the size of the tetrabasic lead sulfate seed crystals.
3. The method of claim 1 , wherein the sulfuric acid is diluted.
4. The method of claim 1 , wherein the sulfuric acid is added over a 10 minute period.
5. The method of claim 3 , further comprising the step of reducing the size of the tetrabasic lead sulfate seed crystals.
6. The method of claim 1 , wherein the tetrabasic lead sulfate seed crystals are reduced in size by milling.
7. The method of claim 1 , wherein the lead oxide paste includes lead monoxide.
8. The method of claim 1 , wherein the tetrabasic lead sulfate seed crystals are loaded into the paste in the range of 0.5 to 10 percent by weight.
9. A method of making a battery paste comprising the step of reacting a mixture of:
water;
lead oxide; and
sulfuric acid;
in the presence of tetrabasic lead sulfate seed crystals.
10. The method of claim 9 , wherein the mixture includes 0.1 to 10 percent loading of seed crystals.
11. A method of making a battery plate, comprising the steps of:
mixing tetrabasic lead sulfate seed crystals with a paste mix to create a battery paste;
wherein the mixing step includes mixing lead oxide, sulfuric acid, and water in the presence of the tetrabasic lead sulfate seed crystals; and
curing the battery paste.
12. The method of claim 1 , wherein the tetrabasic lead sulfate seed crystals have a particle size less than about 2.5 micrometers.
13. The method of claim 5 , wherein the tetrabasic lead sulfate seed crystals have a particle size of approximately 1 micrometers.
14. The method of claim 6 , wherein the tetrabasic lead sulfate seed crystals have a particle size between 2 to 5 micrometers.
15. The method of claim 9 , wherein the tetrabasic lead sulfate seed crystals have a particle size between 2 to 5 micrometers.
16. The method of claim 11 , wherein the tetrabasic lead sulfate seed crystals have a particle size between 2 to 5 micrometers.
17. The method of claim 11 , wherein the step of mixing tetrabasic lead sulfate seed crystals with a paste mix to create a battery paste comprises the step of adding the tetrabasic lead sulfate seed crystals to the paste mix at a loading level of approximately 0.5 to 10 percent.
18. A battery paste comprising:
a battery paste mix;
tetrabasic lead sulfate; and
an oxide.
19. The paste of claim 18 , wherein the tetrabasic lead sulfate is loaded in the battery paste mix at a level of approximately 0.5 to 10 percent.
20. The paste of claim 18 , wherein tetrabasic lead sulfate has a particle size between 2 to 5 micrometers.
21. The paste of claim 18 , wherein the tetrabasic lead sulfate promotes the formation of more tetrabasic lead sulfate in the battery paste during paste mixing.
22. A battery paste comprising:
water;
lead oxide;
sulfuric acid; and
tetrabasic lead sulfate.
23. The battery paste of claim 22 , wherein the tetrabasic lead sulfate is added to promote the formation of tetrabasic lead sulfate in the battery paste.
24. A battery plate made by the method of:
providing the battery paste of claim 22 , wherein the battery paste is formed using tetrabasic seed crystals; and
curing the battery paste.
25. The battery paste of claim 22 , wherein the battery paste is formed by adding tetrabasic lead sulfate particles to a paste mix.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080109325A1 (en) * | 1999-06-03 | 2008-05-08 | Cella Charles H | Contingency-based options and futures for contingent travel accommodations |
CN109742348A (en) * | 2018-12-27 | 2019-05-10 | 浙江天能动力能源有限公司 | A kind of anode diachylon and preparation method thereof adjusting the lead carbon battery capacity service life |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100828275B1 (en) * | 2003-10-21 | 2008-05-07 | 존슨 컨트롤스 테크놀러지 컴퍼니 | Battery Paste Material and Method |
US7118830B1 (en) * | 2004-03-23 | 2006-10-10 | Hammond Group, Inc. | Battery paste additive and method for producing battery plates |
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US20060110524A1 (en) * | 2004-11-19 | 2006-05-25 | Delphi Technologies, Inc. | Additives and modified tetrabasic sulfate crystal positive plates for lead acid batteries |
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DE102008062765A1 (en) | 2008-12-18 | 2010-07-01 | Vb Autobatterie Gmbh & Co. Kgaa | Textile sheet material for a battery electrode |
JP2012519357A (en) | 2009-02-26 | 2012-08-23 | ジョンソン コントロールズ テクノロジー カンパニー | Battery electrode and manufacturing method thereof |
RU2534129C2 (en) | 2009-09-29 | 2014-11-27 | Джордж Э МАЙЕР | Mixture of basic lead sulphates |
US10756335B2 (en) | 2009-09-29 | 2020-08-25 | George E. Mayer | Mixture of basic lead sulfates |
JP5533032B2 (en) * | 2010-03-01 | 2014-06-25 | 新神戸電機株式会社 | Paste type positive electrode plate |
US10522883B2 (en) * | 2010-05-10 | 2019-12-31 | Rsr Technologies, Inc. | Recycling electrochemical cells and batteries |
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CN114204033A (en) * | 2021-12-28 | 2022-03-18 | 河南超威正效电源有限公司 | Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate |
Citations (93)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1572586A (en) * | 1923-11-06 | 1926-02-09 | Prest O Lite Co Inc | Composition for storage-battery electrodes and process of making the same |
US2159226A (en) * | 1935-01-31 | 1939-05-23 | U S L Battery Corp | Electric storage battery plate and a method of treating such plate |
US2165944A (en) * | 1937-05-22 | 1939-07-11 | Gen Chemical Corp | Manufacture of arsenic acid |
US2686213A (en) * | 1953-02-12 | 1954-08-10 | Electric Storage Battery Co | Battery plate and method of making same |
US2872333A (en) * | 1957-06-03 | 1959-02-03 | Clovis H Adams | Pyrotechnic method for increasing the basicity of lead sulfate containing pigments |
US3072693A (en) * | 1955-12-22 | 1963-01-08 | Chemische Fabrik Hoesch Kg | Basic complex lead compounds |
US3169890A (en) * | 1960-12-16 | 1965-02-16 | Varta Ag | Active material for a lead-acid storage battery plate |
US3173810A (en) * | 1960-12-24 | 1965-03-16 | Varta Ag | Manufacture of lead-acid storage battery plates |
US3186871A (en) * | 1959-01-22 | 1965-06-01 | Electric Storage Battery Co | Method for producing porous sintered plate |
US3194685A (en) * | 1964-03-09 | 1965-07-13 | Electric Storage Battery Co | Method of manufacturing storage battery electrode active material |
US3252764A (en) * | 1963-12-13 | 1966-05-24 | Grace W R & Co | Apparatus for producing a fertilizer slurry |
US3312647A (en) * | 1955-12-22 | 1967-04-04 | Chemische Fabrik Hoesch Kg | Vinyl polymer with basic complex lead compound |
US3323859A (en) * | 1963-10-10 | 1967-06-06 | Chemische Fabrik Hoesch Kg | Process for the preparation of dibasic lead salts of inorganic acids |
US3384458A (en) * | 1965-06-16 | 1968-05-21 | Continental Oil Co | Water hydrolysis reactor for making alumina |
US3398024A (en) * | 1965-12-30 | 1968-08-20 | Lucas Industries Ltd | Battery plates |
US3449166A (en) * | 1966-03-08 | 1969-06-10 | Sonnenschein Accumulatoren | Process for the production of filling materials for galvanic elements |
US3552916A (en) * | 1966-11-04 | 1971-01-05 | Nat Lead Co | Acicular anhydrous tribasic lead sulfate and its method of preparation |
US3734694A (en) * | 1968-04-25 | 1973-05-22 | Gen Electric | Apparatus for producing uo2 powder |
US3747560A (en) * | 1967-02-17 | 1973-07-24 | Lucas Industries Ltd | Battery plate coating apparatus |
US3788898A (en) * | 1972-06-07 | 1974-01-29 | Bell Telephone Labor Inc | Fabrication of negative electrodes in lead-acid batteries |
US3819412A (en) * | 1972-02-07 | 1974-06-25 | Tyco Laboratories Inc | Plates for lead acid batteries |
US3862066A (en) * | 1971-05-26 | 1975-01-21 | Universal Pvc Resins | Method for making rigid vinyl chloride polymer compounds |
US3864169A (en) * | 1973-02-13 | 1975-02-04 | Nl Industries Inc | A method for making laminated electrodes |
US3881954A (en) * | 1974-03-18 | 1975-05-06 | Westinghouse Electric Corp | Method of producing a lead dioxide battery plate |
US3887693A (en) * | 1972-05-26 | 1975-06-03 | Derivados Del Fluor Sa | Continuous process for obtaining aluminium fluoride by reacting fluosilicic acid with an aluminous material |
US3894886A (en) * | 1972-04-17 | 1975-07-15 | Gates Rubber Co | Apparatus for pasting battery plates |
US3942433A (en) * | 1972-07-07 | 1976-03-09 | Maschinenfabrik Andritz Ag | Roller arrangement in presses for the removal of water from materials |
US3951688A (en) * | 1972-04-17 | 1976-04-20 | The Gates Rubber Company | Method and apparatus for pasting battery plates |
US4019431A (en) * | 1973-03-17 | 1977-04-26 | Alb. Klein Kg | Method of dewatering sludge |
US4020882A (en) * | 1975-10-20 | 1977-05-03 | Chloride Group Limited | Manufacture of battery plates |
US4024055A (en) * | 1974-08-01 | 1977-05-17 | Globe-Union Inc. | Method of reducing lead and acid waste contamination in battery plant operation |
US4140589A (en) * | 1977-03-28 | 1979-02-20 | Solargen Electronics, Ltd. | Method for lead crystal storage cells and storage devices made therefrom |
US4143218A (en) * | 1976-09-14 | 1979-03-06 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Polymeric materials |
US4159975A (en) * | 1976-12-16 | 1979-07-03 | Akzona Incorporated | Polyether lubricants for use in the processing of plastics |
US4212179A (en) * | 1978-10-12 | 1980-07-15 | The Gates Rubber Company | Driven mandrel and method |
US4315829A (en) * | 1978-01-27 | 1982-02-16 | Exide Corporation | Method of preparing a battery paste containing fibrous polyfluoroethylene for use in the plates of a lead-acid storage battery |
US4319002A (en) * | 1978-02-28 | 1982-03-09 | Hooker Chemicals & Plastics Corp. | Vinyl halide polymer blends of enhanced impact resistance |
US4323470A (en) * | 1980-08-25 | 1982-04-06 | Globe-Union Inc. | Battery paste for lead-acid storage batteries |
US4324768A (en) * | 1977-11-12 | 1982-04-13 | Mizusawa Kagaku Kozyo Kabushiki Kaisha | Process for preparation of lead compounds |
US4326017A (en) * | 1981-01-26 | 1982-04-20 | General Electric Company | Positive electrode for lead acid battery |
US4331516A (en) * | 1980-12-03 | 1982-05-25 | Eltra Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4336236A (en) * | 1981-03-25 | 1982-06-22 | Nl Industries, Inc. | Double precipitation reaction for the formation of high purity basic lead carbonate and high purity normal lead carbonate |
US4338163A (en) * | 1980-12-03 | 1982-07-06 | Eltra Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4381250A (en) * | 1980-12-03 | 1983-04-26 | Allied Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4383011A (en) * | 1980-12-29 | 1983-05-10 | The Gates Rubber Company | Multicell recombining lead-acid battery |
US4387142A (en) * | 1979-01-30 | 1983-06-07 | Lindholm Alfons S M | Granular material consisting of microporous hollow granules of lead powder |
US4387911A (en) * | 1979-03-08 | 1983-06-14 | Juichiro Takada | Seat belt system using lap belt having energy absorption capacity |
US4388210A (en) * | 1979-11-19 | 1983-06-14 | St. Joe Minerals Corporation | High surface area lead oxide composite and method for making the same |
US4501669A (en) * | 1982-01-04 | 1985-02-26 | Axel Johnson Engineering Ab | Method and apparatus for removing liquid from a suspension |
US4507372A (en) * | 1983-04-25 | 1985-03-26 | California Institute Of Technology | Positive battery plate |
US4637966A (en) * | 1983-10-21 | 1987-01-20 | Gates Energy Products, Inc. | Sealed lead-acid cell |
US4648177A (en) * | 1983-10-21 | 1987-03-10 | Gates Energy Products, Inc. | Method for producing a sealed lead-acid cell |
US4656706A (en) * | 1986-01-06 | 1987-04-14 | Globe-Union, Inc. | Formation efficiency of positive plates of a lead-acid battery |
US4758372A (en) * | 1983-05-21 | 1988-07-19 | Hubert Eirich | Method of producing lead paste for batteries |
US4900643A (en) * | 1988-04-08 | 1990-02-13 | Globe-Union Inc. | Lead acid bipolar battery plate and method of making the same |
US4902532A (en) * | 1989-08-03 | 1990-02-20 | Gates Energy Products, Inc. | Method for preparing lead-acid electrochemical cell electrode plates |
US5017446A (en) * | 1989-10-24 | 1991-05-21 | Globe-Union Inc. | Electrodes containing conductive metal oxides |
US5021166A (en) * | 1988-09-30 | 1991-06-04 | Patrick Torpey | Method and an apparatus for extracting a liquid from a sludge |
US5022700A (en) * | 1990-07-19 | 1991-06-11 | Auto Wrap, Inc. | Mounting system for an automobile cover |
US5091273A (en) * | 1990-06-11 | 1992-02-25 | Optima Batteries, Inc. | Method of applying a tail wrap to a wound electrochemical cell and cell produced by the method |
US5092404A (en) * | 1989-11-01 | 1992-03-03 | Marathon Oil Company | Polyvinyl sulfonate scale inhibitor |
US5096611A (en) * | 1989-05-25 | 1992-03-17 | Globe-Union Inc. | Process for the production of battery paste |
US5120620A (en) * | 1990-08-24 | 1992-06-09 | Gates Energy Products, Inc. | Binary lead-tin alloy substrate for lead-acid electrochemical cells |
US5198313A (en) * | 1989-06-14 | 1993-03-30 | Bolder Battery, Inc. | Battery end connector |
US5302476A (en) * | 1990-12-03 | 1994-04-12 | Globe-Union Inc. | High performance positive electrode for a lead-acid battery |
US5314766A (en) * | 1992-10-19 | 1994-05-24 | General Motors Corporation | Lead-acid battery electrode and method of manufacture |
US5382482A (en) * | 1992-08-07 | 1995-01-17 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
US5384217A (en) * | 1992-07-06 | 1995-01-24 | Globe-Union Inc. | Battery plates having rounded lower corners |
US5426144A (en) * | 1993-08-11 | 1995-06-20 | Alliedsignal Inc. | External lubricant and stabilizer compositions for rigid vinyl polymers |
US5434025A (en) * | 1991-03-26 | 1995-07-18 | Gnb Battery Technologies Inc. | Battery grids and plates and lead-acid batteries made using such grids and plates |
US5652074A (en) * | 1996-01-11 | 1997-07-29 | Gnb Technologies, Inc. | Battery grids, a method for making such battery grids and lead-acid batteries using such battery grids |
US5750608A (en) * | 1993-08-11 | 1998-05-12 | Alliedsignal Inc. | External lubricant compositions for rigid vinyl polymers |
US5871862A (en) * | 1997-05-08 | 1999-02-16 | Optima Batteries, Inc. | Battery paste compositions and electrochemical cells for use therewith |
US5874186A (en) * | 1991-03-26 | 1999-02-23 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
US6014798A (en) * | 1998-01-05 | 2000-01-18 | Accumulatorenwerke Hoppecke Carol Zoellner | Method and device for manufacturing lead plates for lead/acid batteries |
US6036945A (en) * | 1997-04-11 | 2000-03-14 | Shamrock Technologies, Inc. | Delivery systems for active ingredients including sunscreen actives and methods of making same |
US6168661B1 (en) * | 1998-04-10 | 2001-01-02 | Johnson Controls Technology Company | Battery cell coating apparatus and method |
US6180286B1 (en) * | 1991-03-26 | 2001-01-30 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
US6228527B1 (en) * | 1999-03-02 | 2001-05-08 | The United States Of America As Represented By The Secretary Of The Navy | Magnesium solution phase catholyte seawater electrochemical system |
US6414071B1 (en) * | 1999-07-29 | 2002-07-02 | Pq Corporation | Aluminosilicate stabilized halogenated polymers |
US20030030042A1 (en) * | 2000-01-11 | 2003-02-13 | Hiroshi Sawada | Zinc borate, and production method and use thereof |
US6531526B1 (en) * | 1998-09-10 | 2003-03-11 | Noveon Ip Holdings Corp. | Halogen containing polymer compounds containing modified zeolite stabilizers |
US20030106205A1 (en) * | 2001-12-10 | 2003-06-12 | Daxing Ma | Paste composition for lead acid battery |
US6749950B2 (en) * | 2002-03-28 | 2004-06-15 | Delphi Technologies, Inc. | Expanded grid |
US20040121233A1 (en) * | 2002-12-24 | 2004-06-24 | Penarroya Oxide Gmbh | Additive for producing a positive active material for lead-acid storage batteries, a method for its production and a method for its use |
US6755874B2 (en) * | 2001-01-11 | 2004-06-29 | Delphi Technologies, Inc. | Plate making process for lead acid battery |
US20040147660A1 (en) * | 2001-07-26 | 2004-07-29 | Hitoshi Ishida | Alkaline earth metal-basic silicate particle |
US20050002373A1 (en) * | 1999-09-22 | 2005-01-06 | Matsushita Electric Industrial Co., Ltd. | Wireless network system and communication method employing both contention mode and contention-free mode |
US20050048372A1 (en) * | 2002-02-21 | 2005-03-03 | Delphi Technologies, Inc. | Electrode |
US7011805B2 (en) * | 2004-03-19 | 2006-03-14 | Ges Technologies Ip Gmbh | Production of tetrabasic lead sulfate from solid state reactions for the preparation of active plates to be used in lead-acid batteries |
US20060093912A1 (en) * | 2004-09-23 | 2006-05-04 | Mayer George E | Paste curing additive |
US20060110524A1 (en) * | 2004-11-19 | 2006-05-25 | Delphi Technologies, Inc. | Additives and modified tetrabasic sulfate crystal positive plates for lead acid batteries |
US7517370B2 (en) * | 2003-10-21 | 2009-04-14 | Johnson Controls Technology Company | Battery paste material and method |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2182479A (en) | 1936-01-30 | 1939-12-05 | Glidden Co | Lead oxide and method of preparation |
US2479603A (en) * | 1944-08-24 | 1949-08-23 | Eagle Picher Co | Storage battery plate and process for making the same |
US2717903A (en) | 1950-05-26 | 1955-09-13 | Olin Mathieson | Nitration of glycerine |
US3001013A (en) | 1955-08-04 | 1961-09-19 | Austin N Stanton | Optical translating system |
US3104946A (en) | 1959-12-28 | 1963-09-24 | Phillips Petroleum Co | Manufacture of wet process phosphoric acid |
BE12203A (en) | 1961-01-04 | |||
US3419431A (en) | 1964-01-27 | 1968-12-31 | Amicon Corp | Polyelectrolyte gel separator and battery therewith |
DE1596322A1 (en) | 1966-02-12 | 1971-07-01 | Waldhof Aschaffenburg Papier | Process for improving the adhesion of particles embedded in the active material of the lead electrodes to the active material |
DE1694676C3 (en) | 1966-04-06 | 1979-08-30 | Lindgens & Soehne, 5000 Koeln | Use of lead carbonate modified with basic lead sulphate as a heat stabilizer for polyvinyl chloride |
US3779962A (en) | 1970-10-09 | 1973-12-18 | G Koenen | Stabilizer-lubricant combinations for halogen-containing polymers |
US3765943A (en) | 1970-12-09 | 1973-10-16 | Bell Telephone Labor Inc | Fabrication of lead-acid batteries |
US4000100A (en) | 1971-06-04 | 1976-12-28 | W. R. Grace & Co. | Thermal and light stabilized polyvinyl chloride resins |
US3702265A (en) | 1971-06-25 | 1972-11-07 | Gen Motors Corp | Lead-acid storage battery paste |
US3770507A (en) | 1972-01-24 | 1973-11-06 | Globe Union Inc | Electrochemical battery employing bonded lead dioxide electrode and fluoroboric acid electrolyte |
US3973991A (en) | 1973-02-13 | 1976-08-10 | Nl Industries, Inc. | Light-weight lead-acid battery with laminated electrodes |
CH563867A5 (en) | 1973-03-01 | 1975-07-15 | Escher Wyss Gmbh | |
US3899349A (en) * | 1974-02-06 | 1975-08-12 | Bell Telephone Labor Inc | Carbon dioxide curing of plates for lead-acid batteries |
US4110519A (en) | 1975-12-29 | 1978-08-29 | Aktiebolaget Tudor | Method for the production of electrodes for lead storage batteries |
NZ183268A (en) | 1976-02-19 | 1978-09-20 | Gould Inc | Process for recycling junk lead-acid batteries comprising the formation of lead carbonate lead monoxide |
US4050482A (en) | 1976-03-31 | 1977-09-27 | The Gates Rubber Company | Battery plate pasting method and apparatus |
US4064725A (en) | 1976-10-18 | 1977-12-27 | The Gates Rubber Company | Apparatus for making spirally wound electrochemical cells |
DE2723946C3 (en) | 1977-05-27 | 1982-04-22 | Nordiska Ackumulatorfabriker Noack AB, Stockholm | Use of plastic coatings to prevent dust formation in the manufacture of electrode plates for lead-acid batteries |
US4346022A (en) | 1979-04-13 | 1982-08-24 | General Electric Company | Method and apparatus for preparing lead-acid battery pastes |
US4423188A (en) | 1980-07-28 | 1983-12-27 | Occidental Chemical Corporation | Vinyl halide polymer blends of enhanced impact resistance |
US4422917A (en) | 1980-09-10 | 1983-12-27 | Imi Marston Limited | Electrode material, electrode and electrochemical cell |
US4407911A (en) | 1980-10-01 | 1983-10-04 | General Electric Company | Rechargeable electrochemical cell pack having resistance to impact and vibration |
US4401730A (en) | 1980-10-03 | 1983-08-30 | Gnb Batteries Inc. | Sealed deep cycle lead acid battery |
US4329182A (en) * | 1980-10-14 | 1982-05-11 | Mizusawa Kagaku Kogyo Kabushiki Kaisha | Granular stabilizer for chlorine-containing polymers |
US4346151A (en) | 1980-12-29 | 1982-08-24 | The Gates Rubber Company | Multicell sealed rechargeable battery |
US4697511A (en) | 1981-02-17 | 1987-10-06 | Envirotech Corporation | Composite roll covering for expressing machines |
US4475453A (en) | 1981-02-17 | 1984-10-09 | Envirotech Corporation | Liquid-solid separation utilizing pressure rolls covered with elastomeric layers |
US4421832A (en) | 1981-08-24 | 1983-12-20 | The Gates Rubber Company | Electrochemical cell |
US4414301A (en) | 1981-12-10 | 1983-11-08 | Allied Corporation | Formed separator set for lead acid batteries |
US4414295A (en) | 1982-05-06 | 1983-11-08 | Gates Energy Products, Inc. | Battery separator |
US4415410A (en) | 1983-02-28 | 1983-11-15 | Allied Corporation | Forming of tetrabasic lead sulfate battery electrodes |
US4618478A (en) | 1983-04-29 | 1986-10-21 | Oxide & Chemical Corporation | Apparatus for the production of lead oxide |
US4547443A (en) | 1983-11-14 | 1985-10-15 | Atlantic-Richfield Company | Unitary plate electrode |
US4551401A (en) | 1984-04-13 | 1985-11-05 | Chloride, Inc. | Method of suppressing lead dust |
DE3503819A1 (en) | 1984-12-21 | 1986-06-26 | Sulzer-Escher Wyss GmbH, 7980 Ravensburg | Hydraulic press shoe and its use and operation |
CH669740A5 (en) | 1985-03-18 | 1989-04-14 | Von Roll Ag | |
US4606982A (en) | 1985-05-09 | 1986-08-19 | Gates Energy Products, Inc. | Sealed lead-acid cell and method |
US4713304A (en) | 1986-06-18 | 1987-12-15 | Gnb Incorporated | Method of preparing lead-acid battery plates and lead-acid batteries containing plates so prepared |
US4889778A (en) | 1987-07-29 | 1989-12-26 | C & D Power Systems, Inc. | Alkali metal polysilica gel electrolyte lead-acid battery and method for making the same |
US4780379A (en) | 1987-10-06 | 1988-10-25 | Gates Energy Products, Inc. | Multicell recombinant lead-acid battery with vibration resistant intercell connector |
US4867886A (en) | 1988-07-25 | 1989-09-19 | Westvaco Corporation | Method and apparatus for controlling sludge flocculant flow |
US4973391A (en) * | 1988-08-30 | 1990-11-27 | Osaka Gas Company, Ltd. | Composite polymers of polyaniline with metal phthalocyanine and polyaniline with organic sulfonic acid and nafion |
US5780913A (en) * | 1995-11-14 | 1998-07-14 | Hamamatsu Photonics K.K. | Photoelectric tube using electron beam irradiation diode as anode |
JP2001229920A (en) * | 2000-02-21 | 2001-08-24 | Shin Kobe Electric Mach Co Ltd | Method of manufacturing sealed lead acid battery |
JP2002231234A (en) * | 2001-01-30 | 2002-08-16 | Shin Kobe Electric Mach Co Ltd | Method of preparing paste active material for use in positive electrode |
US6617071B2 (en) * | 2001-05-24 | 2003-09-09 | Delphi Technologies, Inc. | Active material for high power and high energy lead acid batteries and method of manufacture |
-
2004
- 2004-10-21 KR KR1020067009737A patent/KR100828275B1/en active IP Right Grant
- 2004-10-21 MX MXPA06004510A patent/MXPA06004510A/en active IP Right Grant
- 2004-10-21 JP JP2006536747A patent/JP4505464B2/en not_active Expired - Fee Related
- 2004-10-21 US US10/576,427 patent/US7517370B2/en active Active
- 2004-10-21 EP EP04795820A patent/EP1680827B1/en not_active Not-in-force
- 2004-10-21 BR BRPI0415854-7A patent/BRPI0415854B1/en not_active IP Right Cessation
- 2004-10-21 WO PCT/US2004/034710 patent/WO2005043651A1/en active Application Filing
- 2004-10-21 KR KR1020087007034A patent/KR20080031531A/en not_active Application Discontinuation
- 2004-10-21 AT AT04795820T patent/ATE527709T1/en not_active IP Right Cessation
- 2004-10-21 CN CNB200480037336XA patent/CN100527486C/en not_active Expired - Fee Related
-
2007
- 2007-10-09 US US11/907,133 patent/US20080087868A1/en not_active Abandoned
Patent Citations (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1572586A (en) * | 1923-11-06 | 1926-02-09 | Prest O Lite Co Inc | Composition for storage-battery electrodes and process of making the same |
US2159226A (en) * | 1935-01-31 | 1939-05-23 | U S L Battery Corp | Electric storage battery plate and a method of treating such plate |
US2165944A (en) * | 1937-05-22 | 1939-07-11 | Gen Chemical Corp | Manufacture of arsenic acid |
US2686213A (en) * | 1953-02-12 | 1954-08-10 | Electric Storage Battery Co | Battery plate and method of making same |
US3312647A (en) * | 1955-12-22 | 1967-04-04 | Chemische Fabrik Hoesch Kg | Vinyl polymer with basic complex lead compound |
US3072693A (en) * | 1955-12-22 | 1963-01-08 | Chemische Fabrik Hoesch Kg | Basic complex lead compounds |
US2872333A (en) * | 1957-06-03 | 1959-02-03 | Clovis H Adams | Pyrotechnic method for increasing the basicity of lead sulfate containing pigments |
US3186871A (en) * | 1959-01-22 | 1965-06-01 | Electric Storage Battery Co | Method for producing porous sintered plate |
US3169890A (en) * | 1960-12-16 | 1965-02-16 | Varta Ag | Active material for a lead-acid storage battery plate |
US3173810A (en) * | 1960-12-24 | 1965-03-16 | Varta Ag | Manufacture of lead-acid storage battery plates |
US3323859A (en) * | 1963-10-10 | 1967-06-06 | Chemische Fabrik Hoesch Kg | Process for the preparation of dibasic lead salts of inorganic acids |
US3252764A (en) * | 1963-12-13 | 1966-05-24 | Grace W R & Co | Apparatus for producing a fertilizer slurry |
US3194685A (en) * | 1964-03-09 | 1965-07-13 | Electric Storage Battery Co | Method of manufacturing storage battery electrode active material |
US3384458A (en) * | 1965-06-16 | 1968-05-21 | Continental Oil Co | Water hydrolysis reactor for making alumina |
US3398024A (en) * | 1965-12-30 | 1968-08-20 | Lucas Industries Ltd | Battery plates |
US3449166A (en) * | 1966-03-08 | 1969-06-10 | Sonnenschein Accumulatoren | Process for the production of filling materials for galvanic elements |
US3552916A (en) * | 1966-11-04 | 1971-01-05 | Nat Lead Co | Acicular anhydrous tribasic lead sulfate and its method of preparation |
US3747560A (en) * | 1967-02-17 | 1973-07-24 | Lucas Industries Ltd | Battery plate coating apparatus |
US3734694A (en) * | 1968-04-25 | 1973-05-22 | Gen Electric | Apparatus for producing uo2 powder |
US3862066A (en) * | 1971-05-26 | 1975-01-21 | Universal Pvc Resins | Method for making rigid vinyl chloride polymer compounds |
US3819412A (en) * | 1972-02-07 | 1974-06-25 | Tyco Laboratories Inc | Plates for lead acid batteries |
US3951688A (en) * | 1972-04-17 | 1976-04-20 | The Gates Rubber Company | Method and apparatus for pasting battery plates |
US3894886A (en) * | 1972-04-17 | 1975-07-15 | Gates Rubber Co | Apparatus for pasting battery plates |
US3887693A (en) * | 1972-05-26 | 1975-06-03 | Derivados Del Fluor Sa | Continuous process for obtaining aluminium fluoride by reacting fluosilicic acid with an aluminous material |
US3788898A (en) * | 1972-06-07 | 1974-01-29 | Bell Telephone Labor Inc | Fabrication of negative electrodes in lead-acid batteries |
US3942433A (en) * | 1972-07-07 | 1976-03-09 | Maschinenfabrik Andritz Ag | Roller arrangement in presses for the removal of water from materials |
US3864169A (en) * | 1973-02-13 | 1975-02-04 | Nl Industries Inc | A method for making laminated electrodes |
US4019431A (en) * | 1973-03-17 | 1977-04-26 | Alb. Klein Kg | Method of dewatering sludge |
US3881954A (en) * | 1974-03-18 | 1975-05-06 | Westinghouse Electric Corp | Method of producing a lead dioxide battery plate |
US4024055A (en) * | 1974-08-01 | 1977-05-17 | Globe-Union Inc. | Method of reducing lead and acid waste contamination in battery plant operation |
US4020882A (en) * | 1975-10-20 | 1977-05-03 | Chloride Group Limited | Manufacture of battery plates |
US4143218A (en) * | 1976-09-14 | 1979-03-06 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Polymeric materials |
US4159975A (en) * | 1976-12-16 | 1979-07-03 | Akzona Incorporated | Polyether lubricants for use in the processing of plastics |
US4140589A (en) * | 1977-03-28 | 1979-02-20 | Solargen Electronics, Ltd. | Method for lead crystal storage cells and storage devices made therefrom |
US4324768A (en) * | 1977-11-12 | 1982-04-13 | Mizusawa Kagaku Kozyo Kabushiki Kaisha | Process for preparation of lead compounds |
US4315829A (en) * | 1978-01-27 | 1982-02-16 | Exide Corporation | Method of preparing a battery paste containing fibrous polyfluoroethylene for use in the plates of a lead-acid storage battery |
US4319002A (en) * | 1978-02-28 | 1982-03-09 | Hooker Chemicals & Plastics Corp. | Vinyl halide polymer blends of enhanced impact resistance |
US4212179A (en) * | 1978-10-12 | 1980-07-15 | The Gates Rubber Company | Driven mandrel and method |
US4387142A (en) * | 1979-01-30 | 1983-06-07 | Lindholm Alfons S M | Granular material consisting of microporous hollow granules of lead powder |
US4387911A (en) * | 1979-03-08 | 1983-06-14 | Juichiro Takada | Seat belt system using lap belt having energy absorption capacity |
US4388210A (en) * | 1979-11-19 | 1983-06-14 | St. Joe Minerals Corporation | High surface area lead oxide composite and method for making the same |
US4323470A (en) * | 1980-08-25 | 1982-04-06 | Globe-Union Inc. | Battery paste for lead-acid storage batteries |
US4331516A (en) * | 1980-12-03 | 1982-05-25 | Eltra Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4338163A (en) * | 1980-12-03 | 1982-07-06 | Eltra Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4381250A (en) * | 1980-12-03 | 1983-04-26 | Allied Corporation | Curing of tetrabasic lead pasted battery electrodes |
US4383011A (en) * | 1980-12-29 | 1983-05-10 | The Gates Rubber Company | Multicell recombining lead-acid battery |
US4326017A (en) * | 1981-01-26 | 1982-04-20 | General Electric Company | Positive electrode for lead acid battery |
US4336236A (en) * | 1981-03-25 | 1982-06-22 | Nl Industries, Inc. | Double precipitation reaction for the formation of high purity basic lead carbonate and high purity normal lead carbonate |
US4501669A (en) * | 1982-01-04 | 1985-02-26 | Axel Johnson Engineering Ab | Method and apparatus for removing liquid from a suspension |
US4507372A (en) * | 1983-04-25 | 1985-03-26 | California Institute Of Technology | Positive battery plate |
US4758372A (en) * | 1983-05-21 | 1988-07-19 | Hubert Eirich | Method of producing lead paste for batteries |
US4637966A (en) * | 1983-10-21 | 1987-01-20 | Gates Energy Products, Inc. | Sealed lead-acid cell |
US4648177A (en) * | 1983-10-21 | 1987-03-10 | Gates Energy Products, Inc. | Method for producing a sealed lead-acid cell |
US4656706A (en) * | 1986-01-06 | 1987-04-14 | Globe-Union, Inc. | Formation efficiency of positive plates of a lead-acid battery |
US4900643A (en) * | 1988-04-08 | 1990-02-13 | Globe-Union Inc. | Lead acid bipolar battery plate and method of making the same |
US5021166A (en) * | 1988-09-30 | 1991-06-04 | Patrick Torpey | Method and an apparatus for extracting a liquid from a sludge |
US5096611A (en) * | 1989-05-25 | 1992-03-17 | Globe-Union Inc. | Process for the production of battery paste |
US5290359A (en) * | 1989-05-25 | 1994-03-01 | Globe-Union Inc. | Apparatus for production of a battery paste |
US5198313A (en) * | 1989-06-14 | 1993-03-30 | Bolder Battery, Inc. | Battery end connector |
US4902532A (en) * | 1989-08-03 | 1990-02-20 | Gates Energy Products, Inc. | Method for preparing lead-acid electrochemical cell electrode plates |
US5017446A (en) * | 1989-10-24 | 1991-05-21 | Globe-Union Inc. | Electrodes containing conductive metal oxides |
US5092404A (en) * | 1989-11-01 | 1992-03-03 | Marathon Oil Company | Polyvinyl sulfonate scale inhibitor |
US5091273A (en) * | 1990-06-11 | 1992-02-25 | Optima Batteries, Inc. | Method of applying a tail wrap to a wound electrochemical cell and cell produced by the method |
US5022700A (en) * | 1990-07-19 | 1991-06-11 | Auto Wrap, Inc. | Mounting system for an automobile cover |
US5120620A (en) * | 1990-08-24 | 1992-06-09 | Gates Energy Products, Inc. | Binary lead-tin alloy substrate for lead-acid electrochemical cells |
US5302476A (en) * | 1990-12-03 | 1994-04-12 | Globe-Union Inc. | High performance positive electrode for a lead-acid battery |
US5434025A (en) * | 1991-03-26 | 1995-07-18 | Gnb Battery Technologies Inc. | Battery grids and plates and lead-acid batteries made using such grids and plates |
US5874186A (en) * | 1991-03-26 | 1999-02-23 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
US6180286B1 (en) * | 1991-03-26 | 2001-01-30 | Gnb Technologies, Inc. | Lead-acid cells and batteries |
US5384217A (en) * | 1992-07-06 | 1995-01-24 | Globe-Union Inc. | Battery plates having rounded lower corners |
US5540127A (en) * | 1992-07-06 | 1996-07-30 | Globe-Union, Inc. | Process and apparatus for forming battery plates |
USRE36734E (en) * | 1992-07-06 | 2000-06-13 | Johnson Controls Technology Company | Battery plates having rounded lower corners |
US5382482A (en) * | 1992-08-07 | 1995-01-17 | Nippon Oil Company, Limited | Zinc electrode for alkaline storage battery |
US5314766A (en) * | 1992-10-19 | 1994-05-24 | General Motors Corporation | Lead-acid battery electrode and method of manufacture |
US5426144A (en) * | 1993-08-11 | 1995-06-20 | Alliedsignal Inc. | External lubricant and stabilizer compositions for rigid vinyl polymers |
US5750608A (en) * | 1993-08-11 | 1998-05-12 | Alliedsignal Inc. | External lubricant compositions for rigid vinyl polymers |
US5652074A (en) * | 1996-01-11 | 1997-07-29 | Gnb Technologies, Inc. | Battery grids, a method for making such battery grids and lead-acid batteries using such battery grids |
US6036945A (en) * | 1997-04-11 | 2000-03-14 | Shamrock Technologies, Inc. | Delivery systems for active ingredients including sunscreen actives and methods of making same |
US5871862A (en) * | 1997-05-08 | 1999-02-16 | Optima Batteries, Inc. | Battery paste compositions and electrochemical cells for use therewith |
US6014798A (en) * | 1998-01-05 | 2000-01-18 | Accumulatorenwerke Hoppecke Carol Zoellner | Method and device for manufacturing lead plates for lead/acid batteries |
US6168661B1 (en) * | 1998-04-10 | 2001-01-02 | Johnson Controls Technology Company | Battery cell coating apparatus and method |
US6531526B1 (en) * | 1998-09-10 | 2003-03-11 | Noveon Ip Holdings Corp. | Halogen containing polymer compounds containing modified zeolite stabilizers |
US6228527B1 (en) * | 1999-03-02 | 2001-05-08 | The United States Of America As Represented By The Secretary Of The Navy | Magnesium solution phase catholyte seawater electrochemical system |
US6414071B1 (en) * | 1999-07-29 | 2002-07-02 | Pq Corporation | Aluminosilicate stabilized halogenated polymers |
US20050002373A1 (en) * | 1999-09-22 | 2005-01-06 | Matsushita Electric Industrial Co., Ltd. | Wireless network system and communication method employing both contention mode and contention-free mode |
US20030030042A1 (en) * | 2000-01-11 | 2003-02-13 | Hiroshi Sawada | Zinc borate, and production method and use thereof |
US6755874B2 (en) * | 2001-01-11 | 2004-06-29 | Delphi Technologies, Inc. | Plate making process for lead acid battery |
US7041265B2 (en) * | 2001-07-26 | 2006-05-09 | Mizusawa Industrial Chemicals | Alkaline earth metal-basic silicate particle |
US20040147660A1 (en) * | 2001-07-26 | 2004-07-29 | Hitoshi Ishida | Alkaline earth metal-basic silicate particle |
US6733547B2 (en) * | 2001-12-10 | 2004-05-11 | Delphi Technologies, Inc. | Method of making a paste composition for lead acid battery |
US20030106205A1 (en) * | 2001-12-10 | 2003-06-12 | Daxing Ma | Paste composition for lead acid battery |
US20050048372A1 (en) * | 2002-02-21 | 2005-03-03 | Delphi Technologies, Inc. | Electrode |
US6749950B2 (en) * | 2002-03-28 | 2004-06-15 | Delphi Technologies, Inc. | Expanded grid |
US20040121233A1 (en) * | 2002-12-24 | 2004-06-24 | Penarroya Oxide Gmbh | Additive for producing a positive active material for lead-acid storage batteries, a method for its production and a method for its use |
US7517370B2 (en) * | 2003-10-21 | 2009-04-14 | Johnson Controls Technology Company | Battery paste material and method |
US7011805B2 (en) * | 2004-03-19 | 2006-03-14 | Ges Technologies Ip Gmbh | Production of tetrabasic lead sulfate from solid state reactions for the preparation of active plates to be used in lead-acid batteries |
US20060088465A1 (en) * | 2004-03-19 | 2006-04-27 | Ges Technologies Ip Gmbh | Production of tetrabasic lead sulfate from solid state reactions for the preparation of active plates to be used in lead-acid batteries |
US20060093912A1 (en) * | 2004-09-23 | 2006-05-04 | Mayer George E | Paste curing additive |
US20060110524A1 (en) * | 2004-11-19 | 2006-05-25 | Delphi Technologies, Inc. | Additives and modified tetrabasic sulfate crystal positive plates for lead acid batteries |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080109325A1 (en) * | 1999-06-03 | 2008-05-08 | Cella Charles H | Contingency-based options and futures for contingent travel accommodations |
CN109742348A (en) * | 2018-12-27 | 2019-05-10 | 浙江天能动力能源有限公司 | A kind of anode diachylon and preparation method thereof adjusting the lead carbon battery capacity service life |
Also Published As
Publication number | Publication date |
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JP2007509484A (en) | 2007-04-12 |
CN1894810A (en) | 2007-01-10 |
EP1680827B1 (en) | 2011-10-05 |
CN100527486C (en) | 2009-08-12 |
KR20060086434A (en) | 2006-07-31 |
ATE527709T1 (en) | 2011-10-15 |
MXPA06004510A (en) | 2006-07-06 |
JP4505464B2 (en) | 2010-07-21 |
BRPI0415854A (en) | 2007-01-02 |
EP1680827A1 (en) | 2006-07-19 |
US7517370B2 (en) | 2009-04-14 |
US20070269592A1 (en) | 2007-11-22 |
KR20080031531A (en) | 2008-04-08 |
BRPI0415854B1 (en) | 2014-11-18 |
WO2005043651A1 (en) | 2005-05-12 |
KR100828275B1 (en) | 2008-05-07 |
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