Method for manufacturing components of a lead-acid battery

Abstract

In one or more embodiments described herein, a precursor of an electrode active material of a lead-acid battery may be prepared by a method comprising the steps of forming an active material paste and curing the active material paste to form a precursor of an electrode active material of a lead-acid battery. The active material paste may be prepared by combining at least water, an acid, a glass composition having at least 25 weight percent of a single metal oxide, and lead oxide. The metal oxide may be selected from barium oxide, lead oxide, zinc oxide, or antimony oxide.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims priority to U.S. provisional patent application No. 63 / 071,735, the full text of which is incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a battery, and more specifically to a lead-acid battery. Background Technology

[0005] Lead-acid batteries are one of the oldest types of rechargeable batteries, dating back at least to 1859. The ability of lead-acid batteries to deliver high surge content demonstrates that the cells have a relatively large power-to-weight ratio. Although lead-acid batteries may have a small energy-to-volume ratio and a very low energy-to-weight ratio, they remain a viable option today due to their notable power-to-weight ratio.

[0006] Acid stratification and / or active material degradation is a persistent problem in some conventional lead-acid batteries. Therefore, there is a continuing demand for batteries with reduced acid stratification and / or active material degradation. According to one or more embodiments disclosed herein, it has been revealed that the active material of a lead-acid battery formed by a specific method and material can have improved performance. In particular, in one or more embodiments, the precursor of the active material may be formed using a glass composition comprising at least 25 weight percent of a single metal oxide such as barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide.

[0007] According to at least one aspect of the present invention, a method for forming a precursor of an electrode active material for a lead-acid battery comprises the step of forming an active material by a method comprising combining at least water, an acid, a glass composition comprising at least 25 weight percent of a single metal oxide, and lead oxide. The glass composition may be in granular form, and the lead oxide may be in granular form. The metal oxide may be selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide. The method may further comprise the step of curing an active material paste to form a precursor of an electrode active material for a lead-acid battery.

[0008] According to at least another aspect of the present invention, a precursor of an active material for a lead-acid battery may be formed by forming an active material paste by a method comprising combining at least water, an acid, a glass composition comprising at least 25 weight percent of a single metal oxide, and lead oxide. The glass composition may be in granular form. The lead oxide may be in granular form. The metal oxide may be selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide. The precursor of an active material for a lead-acid battery may be further formed by curing the active material paste to form a precursor of an electrode active material for a lead-acid battery.

[0009] According to at least another aspect of the present invention, a lead-acid battery may comprise an electrolyte solution, at least one negative electrode plate, and at least one positive electrode plate. One or both of the at least one negative electrode plate or the at least one positive electrode plate may comprise an active material formed from a precursor of an active material. The precursor of the active material may be formed by a method comprising the step of forming an active material paste by combining at least water, an acid, a glass composition comprising at least 25 weight percent of a single metal oxide, and lead oxide. The glass composition may be in granular form, and the lead oxide may be in granular form. The metal oxide may be selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide. The method may further comprise the step of curing the active material paste to form a precursor of the electrode active material of the lead-acid battery.

[0010] Additional features and advantages of the technology described in the present invention will be described in the following detailed description, and will be partially apparent to those skilled in the art from the description or recognized by practicing the technology as described in the present invention, including the following detailed description, claims, and the attached drawings. Brief explanation of the drawing

[0011] The following detailed description of specific embodiments of the present invention is best understood when read together with the following drawings, wherein similar structures are indicated by similar reference numbers: FIG. 1 schematically depicts a cross-sectional view of a lead-acid battery according to one or more embodiments illustrated and described in the present invention; FIG. 2 graphs the relationship between capacity and the number of cycles during a 3-hour discharge operation for a lead-acid battery according to one or more embodiments illustrated and described in the present invention; and FIG. 3 graphs the relationship between capacity and number of cycles during full discharge operation for a lead-acid battery according to one or more embodiments illustrated and described in the present invention. More detailed references will now be made to various embodiments, some of which are illustrated in the attached drawings. Where possible, the same reference numbers will be used throughout the drawings to denote identical or similar parts. Specific details for implementing the invention

[0012] According to one or more embodiments, the present invention relates to a precursor of an electrode active material for a lead-acid battery. Additional embodiments described herein include a method for forming a precursor of an electrode active material for a lead-acid battery. The precursor of the electrode active material may be formed into an electrode active material.

[0013] Referring to FIG. 1, a lead-acid battery (100) may include the following components: a positive terminal post (124), a negative terminal post (126), one or more positive plates (111), one or more negative plates (113), one or more separators (116), an electrolyte solution (122), and a battery case (114).

[0014] The positive and negative battery terminal posts (124, 126) may refer to electrical contacts used to connect a load or charger to the battery. The positive and negative battery terminal posts (124, 126) may be connected to the positive and negative straps (118, 120), respectively.

[0015] One or more positive plates (111) may include a positive grid (110) that can be coated with a positive active material. Similarly, one or more negative plates (113) may include a negative grid (112) that can be coated with a negative active material. The active material generally constitutes the electrodes of the lead-acid battery (100). The active material may refer to the chemically active component of the electrode. That is, the active material is a component of the electrode that enables the charging and discharging of the lead-acid battery (100). The negative plate (113) is an electrode that is at a lower potential when the circuit is open. The positive plate (111) is an electrode that is at a higher potential when the circuit is open. As used throughout the invention, "electrode" may refer to an electrical conductor, such as a plate, through which electricity enters and exits the lead-acid battery (100). The lead-acid battery (100) may include both a positive and a negative (i.e., a positive plate and a negative plate (111, 113)). During discharge, H + SO4 can be generated at one or more cathode plates (113), transferred to an electrolyte solution (122), and then consumed at one or more anode plates (111). 2- Ions can be consumed on both plates. The opposite may occur during charging. One or more anodes and cathodes can be composed mainly of lead, lead alloy, sponge lead, lead dioxide, and lead sulfate.

[0016] One or more separators (116) can separate one or more positive plates (111) from one or more negative plates (113) to provide efficient current flow. In some embodiments, the separator (116) may be a polymeric membrane forming a microporous layer, such as a polyethylene material. The separator (116) can ensure that the performance of the lead-acid battery (100), including battery energy and power density, cycle life, and safety, is maintained constant. If one or more positive plates (111) are not kept separated from one or more negative plates (113), the lead-acid battery (100) may short-circuit or fail.

[0017] The electrolyte solution (122) may typically comprise an acidic solution, and the acidic solution most commonly comprises sulfuric acid. As used throughout the invention, "electrolyte solution" may refer to a liquid or gel containing ions that can be decomposed by electrolysis. The electrolyte solution (122) may be a substance that dissociates into ions within the solution to acquire the ability to conduct electricity. An electric current may be transmitted by the movement of ions within the solution. According to one or more embodiments, the electrolyte solution (122) may comprise water and sulfuric acid. In some embodiments, the electrolyte solution (122) may comprise more than 10% by weight of sulfuric acid. For example, the electrolyte solution (122) may contain more than 15 wt% sulfuric acid, more than 20 wt% sulfuric acid, more than 25 wt% sulfuric acid, more than 30 wt% sulfuric acid, more than 35 wt% sulfuric acid, more than 40 wt% sulfuric acid, more than 45 wt% sulfuric acid, or more than 50 wt% sulfuric acid. In some embodiments, it is considered that other acids may be present in the electrolyte solution (122) as an alternative to sulfuric acid. The electrolyte solution (122) may be an aqueous electrolyte such that the electrolyte solution (122) contains water as a solvent or medium, or a gelled electrolyte such that the electrolyte solution (122) is a semi-solid such that it may have characteristics ranging from soft and pliable to hard and rough. Additionally, the electrolyte solution (122) may be stored in a glass mat, as in an absorbed glass mat (AGM) type battery.

[0018] The battery case (114) may accommodate one or more positive plates (111), one or more negative plates (113), one or more separators (116), and an electrolyte solution (122). The battery case (114) may include a plastic resin, for example, polypropylene resin.

[0019] To assemble the components of a lead-acid battery (100), one or more positive plates (111) and one or more negative plates (113) may be connected to positive and negative battery terminal posts (124, 126) via positive and negative straps (118, 120). The positive plates and negative plates (111, 113) may be arranged alternately within a battery case (114), and a plurality of separators (116) may be arranged between each positive plate and negative plate (111, 113). The plurality of separators (116) may help to separate each plate from an adjacent plate and prevent short circuits. The positive strap (118) may connect a plurality of positive plates, and the negative strap (120) may connect a plurality of negative plates. The electrolyte solution (122) may fill the space between the battery case (114) or the positive and negative plates (111, 113) or the pores of the positive and negative plates (111, 113). Positive and negative battery terminal posts (124, 126) may extend from the battery case (114) to provide external electrical contacts used to charge and discharge the lead-acid battery (100). Additionally, the lead-acid battery (100) may include a vent (128) to allow excess gas (e.g., hydrogen, oxygen, etc.) generated during the charging cycle to be discharged into the atmosphere. A vent cap (130) prevents the electrolyte solution (122) from flowing out of the battery case (114).

[0020] When the components of the lead-acid battery (100) are assembled, the lead-acid battery (100) may undergo a formation step to apply charge to the lead-acid battery (100) to convert the lead oxide of the positive plate (111) into lead dioxide (PbO2 or lead(IV) oxide) and the lead oxide of the negative plate (113) into lead. Generally, as described in this specification, the pre-charged material that becomes the active material is referred to as a "precursor of the active material."

[0021] After the activation phase, the lead-acid battery (100) can be repeatedly discharged and charged. During battery discharge, the positive and negative active materials may react with sulfuric acid in the electrolyte solution (122) to form lead (II) sulfide (PbSO4). Due to the reaction between the sulfuric acid and the positive and negative active materials, some of the sulfuric acid in the electrolyte solution (122) may be consumed. However, the sulfuric acid may be returned to the electrolyte solution (122) during the charging phase. The reaction between the positive and negative active materials and the sulfuric acid in the electrolyte solution (122) during discharge can be represented by the following equation:

[0022]

[0023] As can be seen from the above equation, electrical energy is generated during discharge. To charge the lead-acid battery (100), voltage is applied from a charging source to reverse the discharge reaction. During charging, lead sulfate can react with oxygen molecules of ionized water in the electrolyte solution (122) to produce lead and lead dioxide. The generated lead dioxide can be deposited on the positive electrode and the generated lead can be deposited on the negative electrode.

[0024] In one or more embodiments, a precursor of the active material is formed from an active material paste. As used throughout the invention, "active material paste" may refer to a paste that hardens to form a precursor of the active material. The positive and negative active material pastes may generally comprise at least lead oxide (PbO or lead(II) oxide) and a liquid such as water. Each positive grid (110) may be coated with a positive active material paste as set forth in this specification, and each negative grid (112) may be a negative as set forth in this specification. It can be coated with an active material paste. After coating, the active material paste can be cured. The anode or cathode grids (110, 112) coated with the cured anode or cathode active material paste, respectively, together form an anode plate precursor or a cathode plate precursor (i.e., an active material precursor). Throughout the invention, "anode active material paste" and "cathode active material paste" may generally be referred to as "active material paste."

[0025] In one or more embodiments, the active material paste may be formed by combining at least water, an acid, a glass composition comprising at least 25 weight percent of a single metal oxide, and lead oxide. According to one or more embodiments, the metal oxide may be selected from lead oxide, barium oxide, zinc oxide, tin oxide, or antimony oxide.

[0026] A method for forming an active material paste will now be described in more detail. According to one or more embodiments, forming an active material paste may involve first combining a glass composition and a dry component such as lead oxide, and then combining the dry component with a wet component such as water and acid.

[0027] As described above, the active material paste may comprise a glass composition comprising at least 25 weight percent of a single metal oxide. Glass may be formed or obtained first, wherein the glass may generally comprise SiO2 and additional metal oxide. According to some embodiments, the glass, generally comprising SiO2, may be reduced to a granular material and combined with the metal oxide. The granular material may then be combined with the metal oxide and heated to return to a glass form containing the metal oxide. Subsequently, the glass containing the metal oxide may be returned to a granular material before being mixed with other dry components. According to other embodiments, the glass may be processed by grinding, milling, crushing, or other methods and then combined with the metal oxide to produce a glass composition. As described herein, according to one or more embodiments, the glass composition may be in a granular form.

[0028] The glass composition may comprise at least 25 weight% of a single metal oxide. For example, the glass composition may comprise at least 27.5 weight% of a single metal oxide, such as at least 30 weight%, at least 32.5 weight%, at least 35 weight%, at least 37.5 weight%, at least 40 weight%, at least 42.5 weight%, at least 45 weight%, at least 47.5 weight%, at least 50 weight%, at least 52.5 weight%, at least 55 weight%, at least 57.5 weight%, at least 60 weight%, at least 62.5 weight%, at least 65 weight%, at least 67.5 weight%, or at least 70 weight% of a single metal oxide. According to one or more embodiments, the metal oxide may be lead oxide, barium oxide, zinc oxide, tin oxide, or antimony oxide. In other embodiments, it is considered that alternative metal oxides may be used instead of lead oxide, barium oxide, zinc oxide, tin oxide, or antimony oxide. In embodiments, it is considered that a number of metal oxides may be combined. Generally, the remainder of the glass that is not a metal oxide may be silica.

[0029] According to one or more embodiments, the metal oxide of the glass composition may be a metal silicate. Generally, the silicate may be any member of an anionic series consisting of silicon and oxygen, and generally the general formula is [SiO₂]. (4-x) ] n And, where 0≤x<2. Metallic silicates refer to glasses containing only silica and a single metal oxide. Such metallic silicates may include lead silicate, bismuth silicate, tin silicate, lithium silicate, magnesium silicate, potassium silicate, strontium silicate, calcium silicate, or a combination thereof.

[0030] In one or more embodiments, the glass composition may be formed from SiO2 and one or more metal oxides. According to one or more embodiments, the glass composition may be formed by applying heat to melt the components to form a liquid composition. For example, lead oxide (PbO) and silicon dioxide (SiO2) may be melted and mixed together to form a liquid composition. According to one or more embodiments, glass may be produced as the heated liquid mixture returns to ambient conditions. Thus, as described herein, a metal silicate “containing” SiO2 and a metal oxide refers to a material formed, for example, from SiO2 and a metal oxide by melting, wherein SiO2 and the metal oxide form a mixed, “matrix-like” structure as generally understood by those skilled in the art.

[0031] As described above, the glass composition may subsequently be crushed to form a granular form of the glass composition. As used throughout the invention, "granular form" may refer to a material comprising an aggregate of distinct solid, macroscopic particles (or granules). In an embodiment, at least 60.0 weight percent of the granules of the glass composition may pass through a size 10 mesh sieve. In an embodiment, at least 90.0 weight percent of the granules of the glass composition may pass through a size 325 mesh sieve. In some embodiments, at least 90.0 weight percent of the granules of the glass composition may have a diameter of less than 325 mesh (or about 45 μm).

[0032] The metal oxide of the glass can remain in an inert state until a wetting component, such as an acid, is added. After the addition of a wetting component, such as an acid, the metal oxide can react with the acid to form various intermediates of lead sulfate, silica, and silica gel. These intermediates (if present in the active material after curing and charging) can absorb a portion of the electrolyte solution (122) and retain it within the active material. This absorption of a portion of the electrolyte solution (122) can provide a reservoir of acid within the active material for use during charging and discharging operations and can reduce the need to mix charges.

[0033] In some embodiments, the metal oxide may be lead oxide. In one or more embodiments, lead oxide may be added to the positive electrode active material paste or the negative electrode active material paste. The glass composition containing lead oxide may include PbO and SiO2 as described above. In some embodiments, the glass composition may be a lead silicate, such as lead monosilicate, lead bisilicate, or tribasic lead silicate. The glass composition may react with sulfuric acid to form a Si-OH gel within the active material structure of the electrode. The Si-OH gel formation may retain acid within the active material structure of the electrode. Unlike other applications where the Si-OH gel is added to the electrolyte to form a solid gel outside the active material, the Si-OH gel formation using the glass composition may be inside the active material. Such gel formation within the active material can increase acid retention within the active material and thus reduce acid stratification.

[0034] In some embodiments, the formation of the Si-OH gel using lead oxide is slower than the formation of the Si-OH gel when silica powder is added directly to the electrolyte. The slower formation of the Si-OH gel does not alter the fluidity of the active material paste, whereas adding silica powder directly to the precursor of the active material paste can undesirably alter the fluidity of the active material paste. Additionally, the addition of lead oxide may allow for the formation of lead sulfate, which is harmless in a lead-acid battery (100), because lead sulfate is one of the typical products during charging and discharging.

[0035] Lead oxide may refer to a group of inorganic compounds having a formula containing lead and oxygen. Some common lead oxides may include lead(II) oxide (PbO), lead(II,IV) oxide (Pb3O4), and lead dioxide (PbO2). Some less common lead oxides are lead(II,IV) oxide (Pb2O3) and Pb 12 O 19 It may include. Additionally, the lead oxide may include black lead oxide (a mixture of PbO and fine powder of metallic Pb). According to one or more embodiments, the lead oxide may be in granular form.

[0036] According to one or more embodiments, the glass composition may be a metal silicate having a composition comprising 40 to 99 weight% PbO and 1.0 to 60 weight% SiO2. For example, the glass composition comprises 40 wt% to 45 wt%, 40 wt% to 50 wt%, 40 wt% to 55 wt%, 40 wt% to 60 wt%, 40 wt% to 65 wt%, 40 wt% to 70 wt%, 40 wt% to 75 wt%, 40 wt% to 80 wt%, 40 wt% to 85 wt%, 40 wt% to 90 wt%, 40 wt% to 95 wt%, 45 wt% to 50 wt%, 45 wt% to 55 wt%, 45 wt% to 60 wt%, 45 wt% to 65 wt%, 45 wt% to 70 wt%, 45 wt% to 75 wt%, 45 wt% to 80 wt%, 45 wt% to 85 wt%, 45 wt% to 90 wt%, 45 wt% to 95 wt%, 45 wt% to 99 wt%, 50 wt% to 55 wt%, 50 wt% to 60 wt%, 50 wt% to 65 wt%, 50 wt% to 70 wt%, 50 wt% to 75 wt%, 50 wt% to 80 wt%, 50 wt% to 85 wt%, 50 wt% to 90 wt%, 50 wt% to 95 wt%, 50 wt% to 99 wt%, 55 wt% to 60 wt%, 55 wt% to 65 wt%, 55 wt% to 70 wt%, 55 wt% to 75 wt%, 55 wt% to 80 wt%, 55 wt% to 85 wt%, 55 wt% to 90 wt%, 55 wt% to 95 wt%, 60 wt% to 99 wt%, 60 wt% to 65 wt%, 60 wt% to 70 wt%, 60 wt% to 75 wt%, 60 wt% to 80 wt%, 60 wt% to 85 wt%, 60 wt% to 90 wt%, 60 wt% to 95 wt%, 60 wt% to 99 wt%, 70 wt% to 70 wt%, 70 wt% to 75 wt%, 70 wt% to 80 wt%, 70 wt% to 85 wt%, 70 wt% to 90 wt%, 70 wt% to 95 wt%,A composition may have 70 wt% to 99 wt%, 75 wt% to 80 wt%, 75 wt% to 85 wt%, 75 wt% to 90 wt%, 75 wt% to 95 wt%, 75 wt% to 99 wt%, 80 wt% to 85 wt%, 80 wt% to 90 wt%, 80 wt% to 95 wt%, 80 wt% to 99 wt%, 85 wt% to 90 wt%, 85 wt% to 95 wt%, 85 wt% to 99 wt%, 90 wt% to 95 wt%, 90 wt% to 99 wt%, or 95 wt% to 99 wt% PbO.

[0037] In one or more embodiments, the glass composition comprises 1 wt% to 60 wt% SiO2, 1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 15 wt%, 1 wt% to 20 wt%, 1 wt% to 25 wt%, 1 wt% to 30 wt%, 1 wt% to 35 wt%, 1 wt% to 40 wt%, 1 wt% to 45 wt%, 1 wt% to 50 wt%, 1 wt% to 55 wt%, 5 wt% to 10 wt%, 5 wt% to 15 wt%, 5 wt% to 20 wt%, 5 wt% to 25 wt%, 5 wt% to 30 wt%, 5 wt% to 35 wt%, 5 wt% to 40 wt%, 5 wt% to 45 wt%, 5 wt% to 50 wt%, 5 wt% to 55 wt%, 5 wt% to 60 wt%, 10 wt% to 15 wt%, 10 wt% to 20 wt%, 10 wt% to 25 wt%, 10 wt% to 30 wt%, 10 wt% to 35 wt%, 10 wt% to 40 wt%, 10 wt% to 45 wt%, 10 wt% to 50 wt%, 10 wt% to 55 wt%, 10 wt% to 60 wt%, 15 wt% to 20 wt%, 15 wt% to 25 wt%, 15 wt% to 30 wt%, 15 wt% to 35 wt%, 15 wt% to 40 wt%, 15 wt% to 45 wt%, 15 wt% to 50 wt%, 15 wt% to 55 wt%, 15 wt% to 60 wt%, 20 wt% to 25 wt%, 20 wt% to 30 wt%, 20 wt% to 35 wt%, 20 wt% to 40 wt%, 20 wt% to 45 wt%, 20 wt% to 50 wt%, 20 wt% to 55 wt%, 20 wt% to 60 wt%, 25 wt% to 30 wt%, 25 wt% to 35 wt%, 25 wt% to 40 wt%, 25 wt% to 45 wt%, 25 wt% to 50 wt%, 25 wt% to 55 wt%, 25 wt% to 60 wt%, 30 wt% to 35 wt%, 30 wt% to 40 wt%, 30 wt% to 45 wt%, 30 wt% to 50 wt%, 30 wt% to 55 wt%,It may be a metal silicate having a composition comprising 30 wt% to 60 wt%, 35 wt% to 40 wt%, 35 wt% to 45 wt%, 35 wt% to 50 wt%, 35 wt% to 55 wt%, 35 wt% to 60 wt%, 40 wt% to 45 wt%, 40 wt% to 50 wt%, 40 wt% to 55 wt%, 40 wt% to 60 wt%, 45 wt% to 50 wt%, 45 wt% to 55 wt%, 45 wt% to 60 wt%, 50 wt% to 55 wt%, 50 wt% to 60 wt%, or 55 wt% to 60 wt% SiO2.

[0038] Lead oxide can cause partial disruption of the direct interconnections of the silica tetrahedra of SiO2, which can be directly linked to each other by oxygen. This partial disruption can lead to indirect linkages of the silica tetrahedra through lead ions, which can reduce the chemical durability of the glass composition. Therefore, the addition of PbO can increase the sensitivity of the silicate to reactions with acids. When an acid is added to the dry component of the active material paste, the H+ ions of the acid may react with PbO before reacting with SiO2. In one or more embodiments, it is considered that this range of PbO may be advantageous because the acid in the active material paste can allow for an ideal reaction between the acid and SiO2. The higher the percentage of PbO to SiO2, the faster the reaction with these Si-O bonds may occur. Therefore, the amount of PbO in the glass composition can determine how reactive the modified SiO2 is to reactions with acids.

[0039] Pure PbO without SiO2 reacts very rapidly with acids to form lead sulfate. Conversely, pure SiO2 without PbO does not react with acids. However, as discussed earlier, SiO3 can be produced from a combination of PbO and SiO2. -It can react with acid to rapidly form a silica sol gel (SiOH). While lead sulfate is a natural byproduct of the chemical reaction that occurs when charging and discharging a lead-acid battery (100), the silica sol gel can be used to prevent acid stratification during the battery's life and to increase acid retention.

[0040] If the amount of PbO is less than 40 wt% or the amount of SiO2 is greater than 60 wt%, the reaction between the glass composition and the acid may be reduced. Consequently, the acid may be less sensitive to reacting with less PbO, and the content of the silica sol gel may be reduced. Conversely, if the amount of PbO is greater than 99 wt%, similarly, there may not be enough SiO2 in the compound to produce a significant amount of acid-retaining silica sol gel, and most of the product will be lead sulfate.

[0041] In some embodiments, the metal oxide may be barium oxide. In one or more embodiments, since barium can contaminate the anode active material, barium oxide may be useful in the cathode active material paste. In these embodiments, the glass composition may include BaO and SiO2 as described above. The glass composition may react to form a barium sulfate and Si-OH gel. Thus, barium oxide may feature advantages similar to lead oxide as described above.

[0042] In another embodiment, the metal oxide may be zinc oxide. In one or more embodiments, zinc oxide may be added to the positive electrode active material paste or the negative electrode active material paste. In these embodiments, the glass composition may include ZnO and SiO2 as described above. The glass composition may react to form zinc sulfate and Si-OH gel. Thus, zinc oxide may be characterized by advantages similar to lead oxide as described above.

[0043] In another embodiment, the metal oxide may be antimony oxide. In one or more embodiments, since antimony can contaminate the cathode active material, antimony oxide may be useful in the anode active material paste. In such embodiments, the glass composition may include Sb2O3 and SiO2 as described above.

[0044] In another embodiment, the metal oxide may be tin oxide. In one or more embodiments, since tin can contaminate the cathode active material, tin oxide may be useful in the anode active material paste. In these embodiments, the glass composition may include Sn2O3 and SiO2 as described above.

[0045] Similar to the metal oxides discussed earlier, when acid is added to the dry material of the active material paste, antimony oxide and tin oxide can slow down the reaction between the acid and SiO2. That is, the acid reacts first with antimony oxide or tin oxide, and since this acts to modify the structure of SiO2, the reaction between the acid and SiO2 can be slowed down. The above reaction will produce antimony sulfate or tin sulfate and a silica sol gel.

[0046] In an embodiment where the metal oxide is antimony oxide, it has been observed that antimony oxide can improve the rechargeability and cycle life of the battery. When antimony oxide is used, in addition to the benefits discussed above, an antimony dopant may be present in the active material, which can lead to an increase in cycle life. However, when antimony oxide is used, the antimony may migrate to the negative plate (113) over time, causing contamination of the negative plate (113). This can lead to higher moisture loss, which can be destructive to sealed VRLA-type batteries. Therefore, antimony oxide may be recommended for use only in immersion-designed batteries.

[0047] According to one or more embodiments, the glass composition may have a composition comprising 25% to 99% by weight of metal oxide. Here, the weight percentage relates to lead oxide, and it is considered that other glass compositions may have a weight percentage outside this range.

[0048] In one or more embodiments, the glass composition is sufficiently devoid of sodium oxide. Sodium oxide may be undesirable because it may not sufficiently delay the reaction between the acid and SiO2 when the dry component is combined with an acid. If the reaction between the acid and SiO2 is not sufficiently delayed, the precursor may be impossible to process using conventional means. Furthermore, since the molar ratio of Na to SiO2 is, for example, twice that present in lead oxide, H₂ in hydrolysis + The reaction between ions and Si-O bonds can proceed much faster. The rapid reaction between sodium oxide and acid can destabilize the precursor electrode paste and may make processing using conventional means impossible.

[0049] The acid used to form the active material paste may be a chemical substance capable of providing protons or accepting electron pairs in a reaction. The acid may neutralize alkalis or dissolve metals. The acid used to form the active material paste may convert a portion of the lead oxide into basic lead sulfate (i.e., monobasic lead sulfate, tribasic lead sulfate, and tetrabasic lead sulfate) and / or lead sulfate, and may form additional lead sulfate compounds during curing and drying. According to one or more embodiments, the acid may include sulfuric acid. In an embodiment, it is considered that other acids may be used as alternatives to sulfuric acid.

[0050] According to one or more embodiments, the glass composition may contain less than 10 wt% of Al2O3. For example, the glass composition may contain less than 9.5 wt%, less than 9.0 wt%, less than 8.0 wt%, less than 7.5 wt%, less than 7.0 wt%, less than 6.5 wt%, less than 6.0 wt%, less than 5.5 wt%, less than 5.0 wt%, less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%, less than 3.0 wt%, less than 2.5 wt%, less than 2.0 wt%, less than 1.5 wt%, less than 1.0 wt%, or less than 0.5 wt% of Al2O3. Additionally, the glass composition may contain less than 0.1 wt% of Al2O3. For example, the glass composition may contain more than 0.2 wt%, more than 0.3 wt%, more than 0.4 wt%, more than 0.5 wt%, or more than 1.0 wt% of Al2O3. In one or more embodiments, this range is considered advantageous because Al2O3 can act as a stabilizer when preparing the glass composition as described above. Al2O3 can prevent phase separation of the glass composition during heating. In addition to Al2O3, other stabilizing additives may be considered. Other stabilizing additives may include MgO, CaO, SrO, BaO, Li2O, Na2O, K2O, Fe2O3, TiO2, CeO2, ZrO2, ZnO, As2O3, or Sb2O3.

[0051] According to one or more embodiments, the weight ratio of glass composition to lead oxide in the active material paste may be 1:200 to 1:3.33. For example, the weight ratio of lead oxide to glass composition in the active material paste is 1:200 to 1:175, 1:200 to 1:150, 1:200 to 1:125, 1:200 to 1:100, 1:200 to 1:75, 1:200 to 1:50, 1:200 to 1:25, 1:200 to 1:10, 1:200 to 1:5, 1:175 to 1:150, 1:175 to 1:125, 1:175 to 1:100, 1:175 to 1:75, 1:175 to 1:50, 1:175 to 1:25, 1:175 to 1:10, 1:175 to 1:5, 1:175 to 1:3.33, 1:150 to 1:125, 1:150 to 1:100, 1:150 to 1:75, 1:150 to 1:50, 1:150 to 1:25, 1:150 to 1:10, 1:150 to 1:5, 1:150 to 1:3.33, 1:125 to 1:100, 1:125 to 1:75, 1:125 to 1:50, 1:125 to 1:25, 1:125 to 1:10, 1:125 to 1:5, 1:125 to 1:3.33, 1:100 to 1:75, 1:100 to 1:50, It may be in the range of 1:100 to 1:25, 1:100 to 1:10, 1:100 to 1:5, 1:100 to 1:3.33, 1:75 to 1:50, 1:75 to 1:25, 1:75 to 1:10, 1:75 to 1:5, 1:75 to 1:3.33, 1:50 to 1:25, 1:50 to 1:10, 1:50 to 1:5, 1:50 to 1:3.33, 1:25 to 1:10, 1:25 to 1:5, 1:25 to 1:3.33, 1:10 to 1:5, 1:10 to 1:3.33, or 1:5 to 1:3.33.

[0052] According to one or more embodiments, the weight ratio of sulfuric acid to lead oxide in the active material paste may be 1:100 to 1:10. For example, the weight ratio of sulfuric acid to lead oxide in the active material paste may be 1:100 to 1:40, 1:100 to 1:30, 1:100 to 1:20, 1:100 to 1:15, 1:40 to 1:30, 1:40 to 1:20, 1:40 to 1:15, 1:40 to 1:10, 1:30 to 1:20, 1:30 to 1:15, 1:30 to 1:10, 1:20 to 1:15, or 1:20 to 1:10.

[0053] According to one or more embodiments, after forming an active material paste, the active material paste can be cured to form a precursor of the active material of the electrode. Curing is a process in which chemical reactions and / or physical actions occur to create a harder, stronger, or more stable bond or material. Some curing processes require maintaining specific temperature and / or humidity levels. Some curing processes may require maintaining specific pressure. However, some curing processes can be performed simply by exposure to ambient conditions.

[0054] In an embodiment, during the curing of the active material paste, lead may be oxidized, lead oxide may be converted into basic lead sulfate and / or lead sulfate, and lead sulfate and lead oxide may be recrystallized. During curing, as the anode and cathode active material pastes dry, contact between the anode and cathode active material pastes and the anode grid (110) and cathode grid (111) may be improved. Curing may result in a more uniform plate structure as well as an increase in pore volume and surface area. Additionally, a glass composition as disclosed herein may increase the formation of lead sulfate crystals during the curing process. Without being bound by any particular theory, the glass composition may also create a silica gel structure in the active material paste during the curing process. Such a silica gel structure may increase the retention of mobile hydronium ions in the electrolyte solution (122) within the pores of the plate. This can, ultimately, help reduce mobile hydronium ions in the electrolyte solution (122) and prevent acid stratification. Again, without being bound by any specific theory, the glass composition in the active material paste can increase the overall solubility and the ability of the active material paste to absorb acid and water, which can modify the cured active material paste to allow for greater retention of mobile hydronium ions in the electrolyte solution (122). The glass composition may include properties similar to silica gel, which can effectively help reduce the effects of acid stratification by allowing the electrode to absorb acid uniformly throughout the lead-acid battery (100).

[0055] According to one or more embodiments, forming the active material paste may further include combining fibers with water, an acid, a glass composition, and lead oxide. The fibers may include polyester, nylon, or modacrylic fibers. The fibers can increase the mechanical strength of the active material paste and, consequently, increase the mechanical strength of the active material paste-coated plate. More specifically, the fibers can reinforce the paste and prevent cracking of the cured active material paste.

[0056] According to one or more embodiments, the method may further include contacting the active material paste with an electrode grid before curing the active material paste. The electrode grid may be a structure to which the formed active material paste is contacted, thereby supporting the active material paste and aiding in the formation of the electrode and its conductivity.

[0057] As described above, in a lead-acid battery (100), more active material may be utilized due to the retention of the electrolyte solution (122) within the active material. However, through repeated circulation, the electrolyte solution (122) may diffuse back from within the active material to a large volume of electrolyte solution (122) that is not within the active material. This diffusion of the electrolyte solution (122) from within the active material to a large volume of electrolyte solution (122) may result in acid stratification or degradation of the active material.

[0058] Current methods for preventing acid stratification in a lead-acid battery (100) may include introducing a mixed charging step into the recharge profile. Such a mixed charging step may involve a high-current charging step to generate electrolysis within the lead-acid battery (100) cell. Electrolysis may generate bubbles in the electrolyte solution (122), which may cause the electrolyte solution (122) to be mixed as the bubbles move to the surface. Alternatively or additionally, fumed silica may be added to the electrolyte solution (122) to form a gel-like electrolyte solution (122), which may prevent acid stratification. In additional embodiments, fumed silica or an AGM separator may be used to immobilize H+ ions and reduce or prevent acid stratification.

[0059] As disclosed in this specification, a precursor of the electrode active material of a lead-acid battery (100) can reduce acid stratification and / or active material degradation. As described in this specification, an active material paste comprising a glass composition containing at least 25 weight percent of a single metal oxide as an additive can reduce the mobility of acid ions in the electrolyte solution (122) once it is cured and placed in the battery. The electrode active material of the lead-acid battery (100) from the active material paste comprising a glass composition containing at least 25 weight percent of a single metal oxide as an additive can absorb a portion of the electrolyte solution (122) and retain it within the active material. This absorption of a portion of the electrolyte solution (122) can provide a reservoir of acid within the active material for use during charging and discharging operations and can reduce the need to mix charges. In addition, the electrode active material of the lead-acid battery (100) from the active material paste containing additives can provide seed crystals after adding acid to the active material paste mixture, thereby promoting the growth of lead sulfate during curing, which can reduce the degradation of the active material.

[0060] Examples

[0061] Various embodiments of the electrode active material precursor for lead-acid batteries will be further clarified by the following examples. The examples are illustrative in nature and should not be understood as limiting the subject matter of the invention.

[0062] Example 1: Lead silicate

[0063] As used in the following examples, a glass composition of lead silicate was mixed with other raw materials (water, acid, and lead oxide) to form an active material paste. The lead silicate had a density of 6.50 g / cm³ to 6.65 g / cm³ and a melting point of 700°C to 784°C. The chemical composition of the lead silicate was 85 + / - 0.8 wt% PbO (lead monoxide) and 15 + / - 0.8 wt% SiO2. The lead silicate may additionally contain trace amounts of other elements and compositions such as iron oxide, zinc oxide, copper oxide, bismuth oxide, or gold.

[0064] Example 2: Manufacturing of a battery using a standard electrode

[0065] The positive and negative active materials were prepared by mixing sulfuric acid, deionized water, lead-containing oxides (PbO and free Pb metal), and organic polymer fiber flock (polyester). The negative active material also contained an expansion agent (a blend of carbon, barium sulfate, and organic lignin).

[0066] The starting materials were mixed in a specific ratio in a planetary mixer (Custom Milling & Consulting 1.5 Planetary) to produce an active material paste. The positive electrode active material paste was formed by combining 1,000 g of lead-containing oxide, 2 g of fiber floc, 100 g of deionized water, and 100 g of sulfuric acid with a specific gravity of 1.4. The negative electrode active material paste was formed by combining 1,000 g of lead-containing oxide, 2 g of fiber floc, 100 g of deionized water, 80 g of sulfuric acid with a specific gravity of 1.4, and 10 g of an expansion agent.

[0067] To produce an active material paste, the dry components (lead-containing oxide, fiber floc, and expansion agent) were mixed in an oil mixer for 2 minutes. Then, deionized water was added and the resulting mixture was mixed for an additional 2 minutes. Finally, sulfuric acid was added dropwise at a rate of 10 g per minute and mixed again for 3 minutes.

[0068] Next, the active material paste was applied to the electrode grid. The electrode grid was a grid of Pb, Pb-Ca, or Pb-Sb alloy. The active material paste was spread over the electrode grid before curing.

[0069] In the curing process, the active material spread on the electrode grid was placed into a curing chamber (TPC Luner CEO-908-4-B-WFR chamber). The curing process began by raising the temperature from ambient conditions to 55°C and 95% relative humidity for 2 hours. Subsequently, the curing chamber was maintained at 55°C and 95% relative humidity for 48 hours to allow for curing. Afterward, drying was initiated by adjusting the curing chamber to 60°C and 30% relative humidity for 6 hours. Finally, the curing chamber was maintained at 60°C and 30% relative humidity for 20 hours to allow for drying.

[0070] Finally, to form a cell, a lead-acid battery was assembled by alternately welding positive and negative plates of the hardened active material to a connecting strap. Polyethylene was placed between the plates to prevent direct contact between the positive and negative active materials. The lead-acid battery of Example 2 was a test cell battery with only one positive plate and two negative plates. The test cell was placed in an acrylonitrile butadiene styrene (ABS) plastic case, and the electrodes were covered with sulfuric acid (electrolyte solution) with a specific gravity of 1.28.

[0071] Examples 3 and 4: Preparation of batteries with added lead silicate

[0072] In this embodiment, the preparation of the battery having lead silicate as an additive of Example 1 was the same as in Example 2, except that the glass composition of lead silicate was also mixed with the dry components (i.e., lead-containing oxide and fiber flock) that formed the anode. In Examples 3 and 4, lead silicate was added in amounts of 1% and 2% by weight, respectively, based on the weight of the lead-containing oxide. That is, Example 3 was prepared in the same manner as Example 2, except that 10g of the lead silicate of Example 1 was added to the dry component mixture that formed the anode. Similarly, Example 4 was prepared in the same manner as Example 2, except that 20g of the lead silicate of Example 1 was added to the dry component mixture that formed the anode.

[0073] Example 5: Comparison of Examples 2-4

[0074] The batteries of Examples 2 to 4 were tested using a Maccor Series 4000 JO1370 battery test unit. Data collected during the first 20 hours of operation are shown in Table 2. The data were normalized so that Example 2 (lead silicate-free) corresponds to 100%.

[0075] [Table 2]

[0076]

[0077] The raw collected data values ​​for Example 2 were normalized, and the raw collected data values ​​for Examples 3 and 4 were normalized as a percentage of the control group's values ​​to indicate the absolute improvement or loss in performance. The presented data show that the modified glass composition after conditioning was improved compared to the control group. While the data were normalized, Examples 2-4 in Table 2 were measured in ampere-hours.

[0078] Therefore, as can be seen in Table 2, Examples 3 and 4 (addition of 1 wt% and 2 wt% lead silicate, respectively) resulted in an increase in lead-acid battery capacity during the initial life.

[0079] Additionally, FIGS. 2 and 3 provide further evidence that the addition of a glass composition containing at least 25 wt% of a single metal oxide provides an increase in lead-acid battery capacity during the initial life. FIG. 2 graphs the 3-hour discharge rate of the battery (200), and FIG. 3 graphs the complete discharge of the battery (300). As can be seen in FIG. 2, batteries having 1 wt% lead silicate (202) (Example 3) and 2 wt% lead silicate (203) (Example 4) exhibit an increase in lead-acid battery capacity during the initial life at a discharge depth (DOD) of approximately 80% and a discharge rate of 3 hours compared to a lead-acid battery (201) without lead silicate (Example 2). Similarly, in FIG. 3, a battery having 1 wt% lead silicate (302) (Example 3) and 2 wt% lead silicate (303) (Example 4) exhibits an increase in the capacity of the lead acid battery during its initial life at approximately 80% depth of discharge (DOD) and full discharge compared to a lead acid battery (301) (Example 2) without lead silicate. In both figures, a battery having 1 wt% lead silicate (202, 302) (Example 3) and 2 wt% lead silicate (203, 303) (Example 4) provides an increase in the capacity of the lead acid battery during its initial life, for example, in the first 20 to 40 charge and discharge cycles, compared to a lead acid battery (201, 301) (Example 2) without a glass composition containing at least 25 wt% single metal oxide.

[0080] Example 6 - Manufacturing of additional batteries

[0081] Four battery test groups were created and tested. Each battery was a BCI, Type 27M with a calcium grid alloy and an embedded glass mat structure. The test groups were designated as A, B, C, and D. Lead silicate was added to the pastes of test groups A, B, and C, while the battery in test group D was manufactured without lead silicate to serve as a control. The amount of lead silicate added to group A was 1 wt% relative to the lead-containing oxide in the anode paste. Group B had 1 wt% added to the cathode paste. Group C had 1 wt% added to both the anode and cathode pastes. Table 1 shows a summary of groups A and B.

[0082] [Table 3]

[0083]

[0084] The remainder of the anode paste was a mixture of lead-containing oxide, tetrabasic lead sulfate seed crystals, sulfuric acid, water, and polyester fibers. The remainder of the cathode paste was a mixture of lead-containing oxide, sulfuric acid, water, polyester fibers, and an expansion agent (a blend of carbon, lignin, and barium sulfate).

[0085] The paste was applied to an expanded lead-calcium alloy grid. The paste density was approximately 4.47 g / cm³, the moisture content was approximately 11%, and the penetration was 2.9 mm. This was within the standard manufacturing specifications and consistent with previous rheological experiments, indicating that the paste properties were not affected by lead silicate at this loading percentage. After pasting the grid, embedded glass mat paper was applied to each side of the plate using a roller. It was then rapidly dried in an oven to reduce the moisture content to approximately 10% before curing. The plate was cured for 9 hours at >95% relative humidity and a temperature of 85°C, followed by an additional 3 hours of holding and drying according to manufacturing specifications. The anodic cured plate had a weight of approximately 150 g, containing 50 g of grid and 100 g of curing material, while the cathodic plate had a weight of 120 g, containing 25 g of grid and 95 g of curing material.

[0086] After curing, the plates were assembled into a Type 27M battery. A polyethylene separator sleeve was placed on the negative plate, and battery elements were stacked at a ratio of 8 positives to 7 negatives per cell. The battery underwent the remaining assembly using the manufacturer's standard procedures. Then, the fully assembled battery was filled with 1.4 g of sulfuric acid per milliliter and electrically charged to the capacity according to the manufacturer's specifications.

[0087] Example 7 - Evaluation of Example 6 Battery

[0088] Before the electrical test, the following measurements were performed on each battery: weight with an average mass of 23 kg; an average open-circuit voltage of 12.75 V; and the specific gravity of each cell was recorded, with an average specific gravity of approximately 1.28 g sulfuric acid per milliliter of electrolyte. There was no significant difference in the weight of the batteries among the four groups.

[0089] Eight of the formed batteries were selected for testing, with two selected from each group. The selected batteries with the smallest difference in relative specific gravity between cells were chosen. To measure the specific gravity as close to the bottom as possible (approximately 5.5 inches) just below the electrolyte surface, holes were drilled in the first and third cells from the anode. This was the approximate length of the sampling tube of the digital hydrometer used for the measurement. Prior to the results mentioned in Fig. 2, reserve capacity and cold crank tests were performed. The profile for reserve capacity was 25 amperes discharge to 10.5 volts or less; followed by 20 amperes charge to 15.3 volts or more; and then 5 amperes charge for 7 hours or 18 volts. The cold cranking profile was 800 amperes discharge to 6 volts at 0°C. The battery was then charged to a 115% plus 15 ampere-hour boost. Stratified results were obtained in C5, C10, C20, and C100 ampere-hour tests, where the batteries were discharged at currents determined by the reserve capacity data of each battery, which were approximately 17A, 9.7A, 5.25A, and 1A, respectively.

[0090] Table 4 shows the measured difference in specific gravity between the top and bottom of the cell. Measurements were taken after charging and before the next discharge. Note that if the difference in specific gravity between the top and bottom of the cell is greater than 0.015 (15 points), stratification is considered to have occurred in the battery.

[0091] [Table 4]

[0092]

[0093] Before discharge, additional charging steps were applied to prevent acid stratification. Specific gravity (top and bottom) was measured before discharge.

[0094] ** Recharge Profile: 115% of discharge energy + 15Ah (boost charge stage).

[0095] *** Specific gravity (SG) was measured in two cells using a digital hydrometer. The reported result is the average value.

[0096] During discharge, although stratification did not occur significantly, the largest difference in the charged battery specific gravity can be observed between the top and bottom of the cell. Battery overcharging is one method of mixing the electrolyte. The data in Table 4 shows the specific gravity measured before discharge. The control batteries in Group D exhibit acid stratification after discharge of C20 and C100. The recharge profile of the returned 115% charge + 15Ah boost charge is not sufficient to mix the acid well in these two cases. These results lead to the following reduction in acid stratification: Additives in both positive active material (PAM) and negative active material (NAM) > NAM only > PAM only > Control group.

[0097] One or more aspects of the present invention are described herein. A first aspect of the present invention may include a method for forming a precursor of an electrode active material of a lead-acid battery, the method comprising: a step of combining at least water, an acid, a glass composition comprising at least 25 weight% of a single metal oxide, and lead oxide; and a step of curing an active material paste to form a precursor of an electrode active material of a lead-acid battery; wherein the glass composition is in the form of granules, the lead oxide is in the form of granules, and the metal oxide is selected from the group consisting of barium oxide; lead oxide; zinc oxide; tin oxide; or antimony oxide.

[0098] A second aspect of the present invention may include a first aspect, wherein the glass composition is a metal silicate having a composition comprising 40% to 99% by weight PbO and 1.0% to 60% by weight SiO2.

[0099] A third aspect of the present invention may include a first aspect, wherein the glass composition comprises 40% to 99% by weight PbO, 1.0% to 60% by weight SiO2, and 0.1% to 10% by weight Al2O3.

[0100] A fourth aspect of the present invention may include any one of the first to third aspects, wherein the acid includes sulfuric acid.

[0101] The fifth aspect of the present invention may include any one of the first to fourth aspects, wherein the weight ratio of the glass composition to the lead oxide in the active material paste is in the range of 1:200 to 1:3.33.

[0102] The sixth aspect of the present invention may include the fourth aspect, wherein the weight ratio of sulfuric acid to lead oxide in the active material paste is in the range of 1:100 to 1:10.

[0103] A seventh aspect of the present invention may include any one of the first to sixth aspects, wherein the step of forming an active material paste further includes the step of combining fibers with water, acid, a glass composition, and lead oxide.

[0104] The eighth aspect of the present invention may include any one of the first to seventh aspects and further includes the step of contacting the active material paste with an electrode grid before curing the active material paste.

[0105] The ninth aspect of the present invention may include any one of the first to eighth aspects, wherein the glass composition comprises at least 25 weight percent of barium oxide.

[0106] The tenth aspect of the present invention may include any one of the first to ninth aspects, wherein the glass composition comprises at least 25 weight percent of lead oxide.

[0107] The eleventh aspect of the present invention may include any one of the first to ten aspects, wherein the glass composition comprises at least 25 weight percent of zinc oxide.

[0108] The 12th aspect of the present invention may include any one of the 1st to 11th aspects, wherein the glass composition comprises at least 25 weight percent of antimony oxide.

[0109] The 13th aspect of the present invention may include any one of the 1st to 12th aspects, wherein the glass composition comprises at least 25 weight percent of tin oxide.

[0110] The 14th aspect of the present invention may include a precursor of an active material for a lead-acid battery, wherein the precursor is formed by a method comprising the step of forming an active material paste by combining at least water, an acid, a glass composition comprising at least 25 weight% of a single metal oxide, and lead oxide; and the step of curing the active material paste to form a precursor of an active material for a lead-acid battery electrode; wherein the glass composition is in the form of granules, the lead oxide is in the form of granules, and the metal oxide is selected from the group consisting of barium oxide; lead oxide; zinc oxide; tin oxide; or antimony oxide.

[0111] The 15th aspect of the present invention may include the 14th aspect, wherein the glass composition is a metal silicate comprising 40% to 99% by weight PbO, 1.0% to 60% by weight SiO2, and less than 10% by weight Al2O3.

[0112] The 16th aspect of the present invention may include the 14th or 15th aspect, wherein the acid includes sulfuric acid.

[0113] The 17th aspect of the present invention may include any one of the 14th to 16th aspects, wherein the weight ratio of the glass composition to the lead oxide in the active material paste is in the range of 1:200 to 1:3.33.

[0114] The 18th aspect of the present invention may include the 16th aspect, and the weight ratio of sulfuric acid to lead oxide in the active material paste is in the range of 1:100 to 1:10.

[0115] The 19th aspect of the present invention may include a lead-acid battery, the lead-acid battery comprising an electrolyte solution; at least one negative electrode plate; and at least one positive electrode plate; wherein one or both of the at least one negative electrode plate or the at least one positive electrode plate comprises an active material formed from a precursor of an active material; the precursor of the active material is formed by a method comprising the step of forming an active material paste by combining at least water, an acid, a glass composition comprising at least 25 weight% of a single metal oxide, and lead oxide; and the step of curing the active material paste to form a precursor of an active material for a lead-acid battery electrode; wherein the glass composition is in a granular form, the lead oxide is in a granular form, and the metal oxide is selected from the group consisting of barium oxide; lead oxide; zinc oxide; tin oxide; or antimony oxide.

[0116] The 20th aspect of the present invention may include the 19th aspect, wherein the electrolyte solution comprises water and sulfuric acid.

[0117] The 21st aspect of the present invention may include the 19th or 20th aspect, wherein the glass composition is a metal silicate comprising 40% to 99% by weight PbO and 1.0% to 60% by weight SiO2.

[0118] Note that one or more of the following claims utilize the term “here” as a transitional phrase. For the purpose of defining the technology, this term is introduced into the claims as an open transitional phrase used to describe a set of characteristics of the structure and should be interpreted in the same way as the more commonly used open preface term “comprising.”

[0119] Any two quantitative values ​​assigned to a characteristic can constitute a range of that characteristic, and it should be understood that all combinations of ranges formed from all mentioned quantitative values ​​of a given characteristic are considered in the present invention.

[0120] Although the subject matter of the present invention has been described in detail with reference to specific embodiments, it should be noted that the various details described in the present invention, even if specific elements are illustrated in each drawing accompanying this specification, should not be construed as implying that such details relate to elements that are essential components of the various embodiments described in the present invention. Rather, the appended claims should be considered the sole expression of the scope of the present invention and the corresponding scope of the various embodiments described in the present invention. Furthermore, it will be apparent that modifications and variations are possible without departing from the appended claims.

Claims

Claim 1 A method for forming a precursor of an electrode active material of a lead-acid battery, comprising: a step of forming an active material paste by combining at least water, an acid, a glass composition comprising at least 70 weight% of a single metal oxide and SiO2, and lead oxide; and a step of curing the active material paste to form a precursor of an electrode active material of a lead-acid battery, wherein the glass composition is in granular form, the lead oxide is in granular form, and the metal oxide is lead oxide. Claim 2 A method according to claim 1, wherein the glass composition is a metal silicate having a composition comprising 70% to 99% by weight PbO and 1.0% to 30% by weight SiO2. Claim 3 A method according to claim 1 or claim 2, wherein the glass composition comprises 70 wt% to 99 wt% PbO, 1.0 wt% to 29.9 wt% SiO2, and 0.1 wt% to 10 wt% Al2O3. Claim 4 A method according to claim 1, wherein the acid comprises sulfuric acid. Claim 5 A method according to claim 4, wherein the weight ratio of sulfuric acid to lead oxide in the active material paste is 1:100 to 1:

10. Claim 6 A method according to claim 1, wherein the weight ratio of the glass composition to the lead oxide in the active material paste is 1:200 to 1:3.

33. Claim 7 A method according to claim 1, wherein the step of forming the active material paste further comprises the step of combining the fiber with water, acid, a glass composition, and lead oxide. Claim 8 A method according to claim 1, further comprising the step of contacting the active material paste with an electrode grid before curing the active material paste. Claim 9 A precursor of a lead-acid battery active material formed by the method of claim 1. Claim 10 A lead-acid battery comprising: an electrolyte solution; at least one negative plate; and at least one positive plate; wherein one or both of the at least one negative plate or the at least one positive plate comprise an active material formed from a precursor of an active material; and wherein the precursor of the active material is formed by the method of claim 1. Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete

Images