Manufacturing method for lead-acid battery components

Abstract

In one or more embodiments described herein, a lead-acid battery electrode active material precursor can be manufactured by a process including forming an active material paste and curing the active material paste to form a lead-acid battery electrode active material precursor. The active material paste can be made by combining at least water, an acid, a glass composition having at least 25% by weight of a single metal oxide, and lead oxide. The metal oxide can be selected from barium oxide, lead oxide, zinc oxide, or antimony oxide.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 071,735, the entirety of which is incorporated herein by reference. [Technical Field]

[0002] This disclosure relates to batteries, and more specifically, to lead-acid batteries. [Background technology]

[0003] 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 mass-to-power ratio. While lead-acid batteries have a low energy-to-volume ratio and a very low energy-to-mass ratio, their remarkable mass-to-power ratio makes them a viable option even today. [Overview of the Initiative]

[0004] In conventional lead-acid batteries, acid stratification and / or degradation of the active material remain persistent problems. Therefore, there is a continuing need for batteries that reduce acid stratification and / or degradation of the active material. According to one or more embodiments currently disclosed, it has been found that active materials in lead-acid batteries formed by certain methods and materials can have improved performance. In particular, in one or more embodiments, the active material precursor may be formed using a glass composition containing at least 25% by mass of a single metal oxide such as barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide.

[0005] According to at least one aspect of this disclosure, a method for forming a precursor of active material for electrodes of a lead-acid battery includes forming an active material paste by combining at least water, an acid, a glass composition containing at least 25% by mass of a single metal oxide, and lead oxide. The glass composition may be granular, and the lead oxide may be granular. The metal oxide may be selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, and antimony oxide. The method may further include curing the active material paste to form a precursor of active material for electrodes of a lead-acid battery.

[0006] According to at least another aspect of this disclosure, a precursor for the active material of 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 containing at least 25% by mass of a single metal oxide, and lead oxide. The glass composition may be granular. The lead oxide may be granular. The metal oxide may be selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide. Alternatively, a precursor for the active material of a lead-acid battery may be formed by curing the active material paste to form a precursor for the active material of the electrodes of the lead-acid battery.

[0007] According to at least another aspect of this disclosure, 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 and at least one positive electrode plate may comprise an active material formed from an active material precursor. The active material precursor 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% by mass of a single metal oxide, and lead oxide. The glass composition may be granular, and the lead oxide may be granular. 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 curing the active material paste to form an active material precursor for the electrodes of the lead-acid battery.

[0008] Further features and advantages of the technology described in this disclosure are described in the following detailed description, some of which will be readily apparent to those skilled in the art from the description, or will be apparent by practicing the technology described in this disclosure, including the following detailed description, claims, and accompanying drawings. [Brief explanation of the drawing]

[0009] The following detailed description of specific embodiments of this disclosure will be best understood in conjunction with the following drawings, and similar structures are indicated by similar reference numerals.

[0010] [Figure 1] Figure 1 schematically shows a cross-sectional view of a lead-acid battery according to one or more embodiments shown and described in this disclosure.

[0011] [Figure 2] Figure 2 is a graph showing the relationship between capacity and cycle count while a lead-acid battery is discharged for 3 hours according to one or more embodiments shown and described in this disclosure.

[0012] [Figure 3] Figure 3 is a graph showing the relationship between capacity and cycle count while a lead-acid battery is fully discharged, according to one or more embodiments shown and described in this disclosure.

[0013] Next, various embodiments are referred to in more detail, some of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals are used throughout the drawings to refer to identical or similar parts. Detailed Description

[0014] This disclosure relates, according to one or more embodiments, to a precursor of an electrode active material for a lead-acid battery. Additional embodiments described herein include a step for forming a precursor of an electrode active material for a lead-acid battery. The electrode active material precursor may be formed into an electrode active material.

[0015] Referring to Figure 1, the lead-acid battery 100 may comprise components such as a positive electrode terminal post 124, a negative electrode terminal post 126, one or more positive electrode plates 111, one or more negative electrode plates 113, one or more separators 116, an electrolyte solution 122, and a battery case 114.

[0016] The positive and negative battery terminal posts 124 and 126 may indicate electrical contacts used to connect a load or charger to the battery. The positive and negative battery terminal posts 124 and 126 may be connected to the positive and negative straps 118 and 120, respectively.

[0017] One or more positive electrode plates 111 may include a positive electrode grid 110 that can be coated with a positive electrode active material. Similarly, one or more negative electrode plates 113 may include a negative electrode grid 112 that can be coated with a negative electrode active material. The active material generally includes the electrodes of the lead-acid battery 100. The active material can refer to the chemically active components of the electrodes. That is, the active material is the component of the electrodes that enables the charging and discharging of the lead-acid battery 100. The negative electrode plate 113 is the electrode that is at a low potential when the circuit is open. The positive electrode plate 111 is the electrode that is at a high potential when the circuit is open. As used throughout this disclosure, “electrode” can refer to, for example, a plate-shaped conductor through which electricity enters and leaves the lead-acid battery 100. The lead-acid battery 100 may include both a positive electrode and a negative electrode (i.e., a positive electrode plate 111 and a negative electrode plate 113). During discharge, H + It may be generated by one or more negative electrode plates 113, transferred to the electrolyte solution 122, and then consumed by one or more positive electrode plates 111, while SO4 2- Ions may be consumed on both plates. The reverse may occur during charging. One or more positive and negative electrodes may be composed mainly of lead, lead alloy, sponge lead, lead dioxide, or lead sulfate.

[0018] One or more separators 116 may separate one or more positive electrode plates 111 from one or more negative electrode plates 113 to provide an efficient current flow. In some embodiments, the separator 116 may be a polymer membrane forming a microporous layer such as a polyethylene material. The separator 116 can maintain the performance of the lead-acid battery 100, including the energy density and power density of the battery, cycle life, and safety. If the one or more positive electrode plates 111 and the one or more negative electrode plates 113 are not separated, the lead-acid battery 100 may short-circuit or malfunction.

[0019] The electrolyte solution 122 may typically include an acid solution, and the acid solution most commonly includes sulfuric acid. As used throughout this disclosure, "electrolyte solution" refers to a liquid or gel that contains ions and can be decomposed by electrolysis. The electrolyte solution 122 may be a substance that dissociates into ions in solution and obtains an electric conductivity. A current may flow due to the movement of ions in the solution. According to one or more embodiments, the electrolyte solution 122 can include water and sulfuric acid. In some embodiments, the electrolyte solution 122 may include sulfuric acid in excess of 10% by mass. For example, the electrolyte solution 122 may include sulfuric acid in excess of 15% by mass, in excess of 20% by mass, in excess of 25% by mass, in excess of 30% by mass, in excess of 35% by mass, in excess of 40% by mass, in excess of 45% by mass, or in excess of 50% by mass. In some embodiments, it is contemplated 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 can have properties ranging from soft and weak to hard and tough. Further, the electrolyte solution 122 may be housed within a glass mat such as in an absorbed glass mat (AGM) type battery.

[0020] 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 be made of a plastic resin such as, for example, polypropylene resin.

[0021] To assemble the components of the 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 111 and the negative plates 113 may be alternately arranged within the battery case 114, and a plurality of separators 116 may be arranged between each of the positive plates 111 and the negative plates 113. The plurality of separators 116 can serve 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 be filled in the battery case 114 or the space between the positive plate 111 and the negative plate 113, or the pores of the positive plate 111 and the negative plate 113. The positive and negative battery terminal posts 124, 126 may extend from the battery case 114 and provide external electrical contacts used to charge and discharge the lead-acid battery 100. Further, the lead-acid battery 100 may include a vent 128 to allow excess gas (such as hydrogen, oxygen, etc.) generated during the charging cycle to be discharged into the atmosphere. The vent cap 130 prevents the electrolyte solution 122 from spilling out of the battery case 114.

[0022] After the components of the lead-acid battery 100 are assembled, a forming process of charging the lead-acid battery 100 may be performed to convert the lead oxide of the positive plate 111 into lead dioxide (PbO2 or lead oxide (IV)) and the lead oxide of the negative plate 113 into lead. In this specification, generally, the material before charging that becomes the active material is referred to as the "precursor of the active material".

[0023] After the forming process, the lead-acid battery 100 may be repeatedly discharged and charged. During discharge of the battery, the positive electrode active material and the negative electrode active material may react with the sulfuric acid in the electrolyte solution 122 to form lead(II) sulfate (PbSO4). When the positive electrode active material and the negative electrode active material react with sulfuric acid, a part of the sulfuric acid in the electrolyte solution 122 may be consumed. However, in the charging process, sulfuric acid may be returned to the electrolyte solution 122. The reaction between the positive electrode active material and the negative electrode active material and the sulfuric acid in the electrolyte solution 122 during discharge can be represented by the following equations. Reaction at the negative electrode: Pb (s) + SO4 2- (aq) <-> PbSO 4(s) + 2e - Reaction at the positive electrode: PbO 2(s) + SO4 2- (aq) + 4H+ + 2e - <-> PbSO 4(s) + 2(H2O) (l)

[0024] As shown by the above equations, electrical energy is generated during discharge. To charge the lead-acid battery 100, a voltage is applied from a charging source to reverse the discharge reaction. During charging, lead sulfate may react with the oxygen molecules of the ionized water in the electrolyte solution 122 to generate lead and lead dioxide. The generated lead dioxide may be deposited on the positive electrode, and the generated lead may be deposited on the negative electrode.

[0025] In one or more embodiments, the active material precursor is formed from an active material paste. As used throughout this disclosure, “active material paste” may refer to a paste that hardens to form an active material precursor. Positive and negative active material pastes may generally contain at least lead oxide (PbO or lead(II) oxide) and a liquid such as water. Each positive electrode grid 110 may be coated with a positive electrode active material paste as defined herein, and each negative electrode grid 112 may be coated with a negative electrode active material paste as defined herein. After coating, the active material paste may harden. Positive and negative electrode grids 110, 112, respectively, coated with the hardened positive or negative active material paste, form a positive or negative electrode plate precursor (i.e., an active material precursor). As used throughout this disclosure, “positive active material paste” and “negative active material paste” may generally refer to “active material paste.”

[0026] In one or more embodiments, the active material paste may be formed by combining at least water, an acid, a glass composition containing at least 25% by mass 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, and antimony oxide.

[0027] Next, a method for forming an active material paste will 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 wetting component such as water and an acid.

[0028] As described above, the active material paste may contain a glass composition comprising at least 25% by mass of a single metal oxide. The glass may be formed first or obtained, and the glass may generally consist of SiO2 and additional metal oxides. According to some embodiments, the glass, generally comprising SiO2, may be made into a granular material or combined with a metal oxide. The granular material may then be combined with a metal oxide, heated, and returned to the form of a glass containing the metal oxide. The glass containing the metal oxide may then be returned to a granular material again before being mixed with other dry components. According to other embodiments, the glass may be pulverized, crushed, broken, or otherwise processed, and then combined with a metal oxide to produce a glass composition. According to one or more embodiments as described herein, the glass composition may be granular.

[0029] The glass composition may contain at least 25% by mass of a single metal oxide. For example, the glass composition may contain at least 27.5% by mass of a single metal oxide, at least 30% by mass of a single metal oxide, at least 32.5% by mass of a single metal oxide, at least 35% by mass of a single metal oxide, at least 37.5% by mass of a single metal oxide, at least 40% by mass of a single metal oxide, at least 42.5% by mass of a single metal oxide, at least 45% by mass of a single metal oxide, or at least 47.5% by mass of a single metal oxide. It may contain at least 50% by mass of a single metal oxide, at least 52.5% by mass of a single metal oxide, at least 55% by mass of a single metal oxide, at least 57.5% by mass of a single metal oxide, at least 60% by mass of a single metal oxide, at least 62.5% by mass of a single metal oxide, at least 65% by mass of a single metal oxide, at least 67.5% by mass of a single metal oxide, or at least 70% by mass 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, alternative metal oxides may be used instead of lead oxide, barium oxide, zinc oxide, tin oxide, or antimony oxide. In embodiments, a combination of multiple metal oxides is intended. Generally, the remainder of the glass that is not a metal oxide may be silica.

[0030] According to one or more embodiments, the metal oxide of the glass composition may be a metal silicate. Generally, silicates have the general formula [SiO₂]. (4-x) ] nx is any component of the family of anions consisting of silicon and oxygen, represented by (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 combinations thereof.

[0031] 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 heating to melt the components and form a liquid composition. For example, lead oxide (PbO) and silicon dioxide (SiO2) may be melted and mixed to form a liquid composition. According to one or more embodiments, when the heated liquid mixture is returned to ambient conditions, glass may be produced. Thus, as described herein, metal silicates "containing" SiO2 and metal oxides refer to materials formed from SiO2 and metal oxides, for example by melting, which form a mixed "matrix-like" structure as generally understood by those skilled in the art.

[0032] As described above, the glass composition may subsequently be ground to form granular glass composition. As used throughout this disclosure, “granular” may refer to a material comprising discrete solids, macroscopic particles (or granules), or aggregates of particles. In embodiments, at least 60.0% by mass of the granules in the granular form of the glass composition may pass through a sieve of size 10 mesh. In embodiments, at least 90.0% by mass of the granules in the granular form of the glass composition may pass through a sieve of size 325 mesh. In some embodiments, at least 90.0% by mass of the granules in the granular form of the glass composition may have a diameter of less than 325 mesh (or about 45 μm).

[0033] The metal oxides in the glass may remain inert until after the addition of a wetting component such as an acid. After the addition of a wetting component such as an acid, the metal oxides can react with the acid to form various intermediates of lead sulfate, silicic acid, and silica gel. These intermediates (which are temporarily present in the active material after curing and charging) can absorb and retain a portion of the electrolyte solution 122. This absorption of a portion of the electrolyte solution 122 can provide a reserve of acid in the active material for use during charging and discharging operations, reducing the need for mixed charging.

[0034] In some embodiments, the metal oxide may be lead oxide. In one or more embodiments, lead oxide may be added to the positive or negative active material paste. The glass composition containing lead oxide may also contain PbO and SiO2, as described above. In embodiments, the glass composition may be lead silicate, such as lead monosilicate, lead disilicate, or lead trisilicate. The glass composition may react with sulfuric acid to form a Si-OH gel within the active material structure of the electrode. Si-OH gel formation can retain acid within the active material structure of the electrode. Unlike other applications where Si-OH gel is added to an electrolyte to form a solid gel outside the active material, Si-OH gel formation with a glass composition may occur within the active material. This gel formation within the active material may increase the acid retention capacity within the active material and suppress acid stratification.

[0035] In some embodiments, the formation of Si-OH gels using lead oxide is slower than the formation of Si-OH gels when silica powder is directly added to the electrolyte. Although the rheology of the active material paste does not change even if the formation of Si-OH gels is slow, the rheology of the active material paste may change undesirably when silica powder is directly added to the precursor of the active material paste. Furthermore, the addition of lead oxide, which may allow the formation of lead sulfate, is harmless in the lead-acid battery 100 because lead sulfate is one of the typical products during charging and discharging.

[0036] Lead oxide can refer to a group of inorganic compounds whose formulas include lead and oxygen. Some common lead oxides may include lead(II) oxide (PbO), lead(II,IV) oxide (Pb3O4), and lead dioxide (PbO2). Less common lead oxides include lead(II,IV) oxide (Pb2O3) and Pb 12 O 19 It may also contain [a specific substance]. Furthermore, the lead oxide may include black lead oxide (a mixture of PbO and finely powdered metallic Pb). According to one or more embodiments, the lead oxide may be granular.

[0037] According to one or more embodiments, the glass composition may be a metal silicate having a composition comprising 40% to 99% by mass of PbO and 1.0% to 60% by mass of SiO2.For example, glass compositions include 40% to 45%, 40% to 50%, 40% to 55%, 40% to 60%, 40% to 65%, 40% to 70%, 40% to 75%, 40% to 80%, 40% to 85%, 40% to 90%, 40% to 95%, 45% to 50%, 45% to 55%, 45% to 60%, 45% to 65%, 45% to 70%, 45% to 75%, and 45%. From 80% by mass, 45% to 85% by mass, 45% to 90% by mass, 45% to 95% by mass, 45% to 99% by mass, 50% to 55% by mass, 50% to 60% by mass, 50% to 65% by mass, 50% to 70% by mass, 50% to 75% by mass, 50% to 80% by mass, 50% to 85% by mass, 50% to 90% by mass, 50% to 95% by mass, 50% to 99% by mass, 55% to 60% by mass, 55% to 65% by mass, 55% to 70% by mass, 55% to 75% by mass mass%, 55% to 80%, 55% to 85%, 55% to 90%, 55% to 95%, 60% to 99%, 60% to 65%, 60% to 70%, 60% to 75%, 60% to 80%, 60% to 85%, 60% to 90%, 60% to 95%, 60% to 99%, 70% to 70%, 70% to 75%, 70% to 80%, 70% to 85%, 70% to 85%, 70% to 90%, The composition may include 70% or 95% by mass, 70% to 99% by mass, 75% to 80% by mass, 75% to 85% by mass, 75% to 90% by mass, 75% to 95% by mass, 75% to 99% by mass, 80% to 85% by mass, 80% to 90% by mass, 80% to 95% by mass, 80% to 99% by mass, 85% to 90% by mass, 85% to 95% by mass, 85% to 99% by mass, 90% to 95% by mass, 90% to 99% by mass, or 95% to 99% by mass of PbO.

[0038] In one or more embodiments, the glass compounds may be metal silicates having a composition containing 1% to 60% by mass of SiO2, such as 1% to 5% by mass, 1% to 10% by mass, 1% to 15% by mass, 1% to 20% by mass, 1% to 25% by mass, 1% to 30% by mass, 1% to 35% by mass, 1% to 40% by mass, 1% to 45% by mass, 1% to 50% by mass, 1% to 55% by mass, 5% to 10% by mass, 5% to 15% by mass, 5% to 20% by mass, 5% to 25% by mass, 5% to 30% by mass, 5% to 35% by mass, 5% to 40% by mass, and 5% to 45% by mass. 5% to 50%, 5% to 55%, 5% to 60%, 10% to 15%, 10% to 20%, 10% to 25%, 10% to 30%, 10% to 35%, 10% to 40%, 10% to 45%, 10% to 50%, 10% to 55%, 10% to 60%, 15% to 20%, 15% to 25%, 15% to 30%, 15% to 35%.15% to 40%, 15% to 45%, 15% to 50%, 15% to 55%, 15% to 60%, 20% to 25%, 20% to 30%, 20% to 35%, 20% to 40%, 20% to 45%, 20% to 50%, 20% to 55%, 20% to 60%, 25% to 30%, 25% to 35%, 25% to 40%, 25% to 45%, 25% to 50%, 25% to 55%, 25% to 60%, 30% to 35%, 30% The metal silicate may have a composition containing 40% by mass, 30% to 45% by mass, 30% to 50% by mass, 30% to 55% by mass, 30% to 60% by mass, 35% to 40% by mass, 35% to 45% by mass, 35% to 50% by mass, 35% to 55% by mass, 35% to 60% by mass, 40% to 45% by mass, 40% to 50% by mass, 40% to 55% by mass, 40% to 60% by mass, 45% to 50% by mass, 45% to 55% by mass, 45% to 60% by mass, 50% to 55% by mass, 50% to 60% by mass, or 55% to 60% by mass of Provider 2.

[0039] Lead oxide can cause partial breakdown of the direct interconnections of silica tetrahedra in SiO2 due to oxygen. This partial breakdown can lead to indirect connections of the silica tetrahedra via lead ions, potentially degrading the chemical durability of the glass composition. Thus, the addition of PbO can improve the reactivity of silicates with acids. When acid is added to the dry components of the active material paste, the acid's H + Ions may react with PbO before reacting with SiO2. Since the acid in the active material paste may allow for an ideal reaction with SiO2, it is intended that such a range of PbO may be beneficial in one or more embodiments. A higher ratio of PbO to SiO2 may result in a faster reaction with this Si-O bond. Therefore, the amount of PbO in the glass composition may determine how the modified SiO2 reacts with the acid.

[0040] Pure PbO without SiO2 will react very quickly with acid to form lead sulfate. Conversely, pure SiO2 without PbO will not react with acid. However, SiO3 will be produced from the combination of PbO and SiO2 as described above. - It may react with acid to rapidly form silica sol gel (SiOH). Lead sulfate is a natural product of the chemical reaction that occurs during the charging and discharging of lead-acid batteries 100, but silica sol gel may be used to prevent acid stratification during the battery life and to increase the acid retention rate.

[0041] If the amount of PbO is 40% by mass or less, or the amount of SiO2 is 60% by mass or more, the reactivity of the glass composition with the acid may decrease. Therefore, if the amount of PbO is low, the acid will not react easily, and the amount of silica sol gel may decrease. Conversely, if the amount of PbO is greater than 99% by mass, similarly, there may not be enough SiO2 in the compound to produce a sufficient amount of silica sol gel that retains the acid, and the majority of the product will be lead sulfate.

[0042] In some embodiments, the metal oxide may be barium oxide. In one or more embodiments, barium oxide may be useful in the negative electrode active paste because barium may poison the positive electrode active material. In such embodiments, the glass composition may contain BaO and SiO2 as described above. The glass composition may react with barium sulfate to form a Si-OH gel. Barium oxide may therefore have similar advantages to lead oxide as described above.

[0043] In further embodiments, the metal oxide may be zinc oxide. In one or more embodiments, zinc oxide may be added to a positively active material paste or a negatively active material paste. In such embodiments, the glass composition may contain ZnO and SiO2 as described above. The glass composition may react with zinc sulfate to form a Si-OH gel. Thus, zinc oxide may have similar advantages to lead oxide as described above.

[0044] In yet another embodiment, the metal oxide may be antimony oxide. In one or more embodiments, antimony oxide may be useful in the positive electrode active material paste because antimony may poison the negative electrode active material. In such embodiments, the glass composition may contain Sb2O3 and SiO2 as described above.

[0045] In further embodiments, the metal oxide may be tin oxide. In one or more embodiments, tin oxide may be useful in the positive electrode active material paste because tin may poison the negative electrode active material. In such embodiments, the glass composition may contain Sn2O3 and SiO2 as described above.

[0046] Similar to the metal oxides mentioned earlier, when an acid is added to the dried 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 may react first with antimony oxide or tin oxide, which may be acting to modify the structure of SiO2, thus slowing down the reaction between the acid and SiO2. This reaction produces a silica sol gel with antimony sulfate or tin sulfate.

[0047] In embodiments 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 using antimony oxide, in addition to the advantages described above, antimony dopants may be present in the active material, which can lead to increased cycle life. However, when using antimony oxide, antimony may migrate to the negative electrode plate 113 over time, causing poisoning of the negative electrode plate 113. This can result in higher water loss, which can be destructive for sealed and VRLA type batteries. Therefore, it is sometimes recommended to use antimony oxide only in batteries with a water-immersion design.

[0048] According to one or more embodiments, the glass composition may have a composition containing 25% to 99% by mass of a metal oxide. Herein, the mass percentage is directed towards lead oxide, but other glass compositions may have mass percentages outside this range.

[0049] In one or more embodiments, the glass composition does not contain sufficient sodium oxide. Sodium oxide can be undesirable because, when mixing the dry components with the acid, it may not sufficiently slow down the reaction between the acid and SiO2. If the reaction between the acid and SiO2 is not sufficiently slowed down, the precursor may not be treatable by conventional means. Furthermore, the molar ratio of Na to SiO2 is, for example, twice that of lead oxide, which can lead to H in hydrolysis. + The reaction between ions and Si-O bonds may proceed more rapidly. Because the reaction between sodium oxide and acid is so fast, the precursor electrode paste may become unstable, potentially making processing impossible using conventional methods.

[0050] The acid used in forming the active material paste may be a chemical substance that has the ability to donate protons or accept electron pairs in the reaction. The acid may also be capable of neutralizing alkalis or dissolving metals. The acid used in forming the active material paste may convert some 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 contain sulfuric acid. In embodiments, other acids may be used as substitutes for sulfuric acid.

[0051] According to one or more embodiments, the glass composition may contain less than 10% by mass of Al2O3. For example, the glass composition may contain less than 9.5% by mass, less than 9.0% by mass, less than 8.0% by mass, less than 7.5% by mass, less than 7.0% by mass, less than 6.5% by mass, less than 6.0% by mass, less than 5.5% by mass, less than 5.0% by mass, less than 4.5% by mass, less than 4.0% by mass, less than 3.5% by mass, less than 3.0% by mass, less than 2.5% by mass, less than 2.0% by mass, less than 1.5% by mass, less than 1.0% by mass, or less than 0.5% by mass of Al2O3. Furthermore, the glass composition may contain less than 0.1% by mass of Al2O3. For example, the glass composition may contain more than 0.2% by mass, more than 0.3% by mass, more than 0.4% by mass, more than 0.5% by mass, or more than 1.0% by mass of Al2O3. Such a range is intended to be beneficial in one or more embodiments, because Al2O3 can function as a stabilizer when preparing glass compositions, as described above. Al2O3 can prevent phase separation in the glass composition during heating. In addition to Al2O3, other stabilizing additives may be used. Other stabilizing additives may include MgO, CaO, SrO, BaO, Li2O, Na2O, K2O, Fe2O3, TiO2, CeO2, ZrO2, ZnO, As2O3, or Sb2O3.

[0052] According to one or more embodiments, the mass ratio of the glass composition to lead oxide in the active material paste may be in the range of 1:200 to 1:3.33. For example, the mass ratio of the glass composition to lead oxide in the active material paste may be 1:200~1:175, 1:200~1:150, 1:200~1:125, 1:200~1:100, 1:200~1:75, 1:200~1:50, 1:200~1:25, 1:200~1:10, 1:200~1:5, 1:175~1:150, 1:175~1:125, 1:17 5~1:100, 1:175~1:75, 1:175~1:50, 1:175~1:25, 1:175~1:10, 1:175~1:5, 1:175~1:3.33, 1:150~1:125, 1:150~1:100, 1:150~1:75, 1:150~1:50, 1:150~1:25, 1:150~1:10, 1:150~1:5, 1:150~ 1:3.33, 1:125~1:100, 1:125~1:75, 1:125~1:50, 1:125~1:25, 1:125~1:10, 1:125~1:5, 1:125~1:3.33, 1:100~1:75, 1:100~1:50, 1:100~1:25, 1:100~1:10, 1:100~1:5, 1:100~3.33, 1:75~1:5 The range may be 0, 1:75~1:25, 1:75~1:10, 1:75~1:5, 1:75~1:3.33, 1:50~1:25, 1:50~1:10, 1:50~1:5, 1:50~1:3.33, 1:25~1:10, 1:25~1:5, 1:25~1:3.33, 1:10~1:5, 1:10~1:3.33, or 1:5~1:3.33.

[0053] According to one or more embodiments, the mass ratio of sulfuric acid to lead oxide in the active material paste may be in the range of 1:100 to 1:10. For example, the mass ratio of sulfuric acid to lead oxide in the active material paste may be in the range of 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.

[0054] According to one or more embodiments, after forming an active material paste, the active material paste may then be cured to form a precursor of the electrode active material. Curing is a process during which chemical reactions and / or physical actions occur, resulting in a harder, stronger, or more stable aggregate or material. Some curing processes require the maintenance of a constant temperature and / or humidity. In some curing processes, it may also be necessary to maintain a certain pressure. However, some curing processes can be carried out simply by exposure to ambient conditions.

[0055] In embodiments, during the curing of the active material paste, lead may oxidize, the lead oxide may be converted to basic lead sulfate and / or lead sulfate, and the lead sulfate and lead oxide may recrystallize. During curing, while the positive electrode active material paste and negative electrode active material paste dry, the contact between the positive electrode grid 110 and the negative electrode grid 111 may be improved. Curing may increase the pore volume and surface area, as well as result in a more uniform plate-like structure. Furthermore, glass compositions such as those disclosed herein may increase the formation of lead sulfate crystals during the curing process. Although not intended to be bound by any particular theory, glass compositions may also generate silica gel structures in the active material paste during the curing process. These silica gel structures may increase the retention of mobile hydronium ions in the electrolyte solution 122 within the pores of the plate. This may reduce the number of mobile hydronium ions in the electrolyte solution 122, which may help counteract acid stratification. Again, without intending to be bound by any particular theory, the glass composition in the active material paste may increase the overall solubility and ability of the active material paste to absorb acid and water, thereby modifying the cured active material paste to better retain mobile hydronium ions in the electrolyte solution 122. The glass composition may also contain properties similar to silica gel, which may effectively help reduce the effects of acid stratification by allowing the electrodes to uniformly absorb acid throughout the lead-acid battery 100.

[0056] According to one or more embodiments, forming an active material paste may further involve combining fibers with water, an acid, a glass composition, and lead oxide. The fibers may consist of polyester fibers, nylon fibers, or modacrylic fibers. The fibers can improve the mechanical strength of the active material paste and, consequently, the mechanical strength of the plate with the active material paste. More specifically, the fibers can reinforce the bond and prevent cracking of the cured active material paste.

[0057] According to one or more embodiments, the method may further include contacting the active material paste with an electrode grid before the active material paste hardens. The electrode grid may be a structure to which the formed active material paste is contacted, thereby providing support for the active material paste and assisting in the conductivity and formation of the electrodes.

[0058] As previously described herein, in the lead-acid battery 100, the utilization rate of the active material can be increased by retaining the electrolyte solution 122 within the active material. However, with repeated cycles, the electrolyte solution 122 may diffuse out of the active material and return to the bulk of the electrolyte solution 122 outside the active material. Such diffusion of the electrolyte solution 122 from the active material back to the bulk can lead to acid stratification or degradation of the active material.

[0059] Current methods to counteract acid stratification in lead-acid batteries 100 may include introducing a mixed charging step into the recharge profile. Such a mixed charging step may include a high-current charging step to induce electrolysis within the cells of lead-acid batteries 100. Electrolysis can generate bubbles in the electrolyte solution 122, which may mix the electrolyte solution 122 as they move to the surface. Alternatively or additionally, fumed silica may be added to the electrolyte solution 122 to form a gel-type electrolyte solution 122, thereby counteracting acid stratification. In additional embodiments, fumed silica or AGM separator is H +It may be used to immobilize ions and reduce or prevent acid stratification.

[0060] As disclosed herein, the precursor of the active material for the electrodes of the lead-acid battery 100 can reduce acid stratification and / or degradation of the active material. As described herein, an active material paste comprising a glass composition containing at least 25% by mass of a single metal oxide as an additive may reduce the mobility of acidic ions in the electrolyte solution 122 once cured and placed in the battery. The active material for the electrodes of the lead-acid battery 100 formed from an active material paste comprising a glass composition containing 25% by mass or more of a single metal oxide as an additive can absorb and retain a portion of the electrolyte solution 122 within the active material. By absorbing a portion of the electrolyte solution 122 in this way, an acid for use during charge-discharge operations can be stored within the active material, reducing the need for mixed charging. Furthermore, the active material for the electrodes of the lead-acid battery 100 derived from an active material paste containing additives may provide seed crystals after the addition of acid to the active material paste mix, promoting the growth of lead sulfate during curing and reducing degradation of the active material. [Examples]

[0061] Various embodiments of the precursor for the active material of lead-acid battery electrodes will be further illustrated by the following examples. These examples are illustrative in nature and should not be understood as limiting the subject matter of this disclosure.

[0062] Example 1. Lead silicate

[0063] As used in the following examples, a lead silicate glass composition 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 to 6.65 grams per cubic centimeter and a melting point of 700°C to 784°C. The chemical composition of the lead silicate was 85 + / - 0.8 mass% PbO (lead monoxide) and 15 + / - 0.8 mass% SiO2. The lead silicate may also contain trace amounts of other elements or compositions, such as iron oxide, zinc oxide, copper oxide, bismuth oxide, gold, etc.

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

[0065] The active materials for the positive and negative electrodes were prepared by mixing sulfuric acid, deionized water, lead oxide (PbO and free Pb metal), and organic polymer fiber flocs (polyester). A swelling agent (a mixture of carbon, barium sulfate, and organic lignin) was also used as the active material for the negative electrode.

[0066] To form the active material paste, the raw materials were mixed in specific ratios using a planetary mixer (Custom Milling & Consulting 1.5 Planetary). The positive active material paste was formed by combining 1000 grams of lead oxide, 2 grams of fiber floc, 100 grams of deionized water, and 100 grams of sulfuric acid with a specific gravity of 1.4. The negative active material paste was formed by combining 1000 grams of lead oxide, 2 grams of fiber floc, 100 grams of deionized water, 80 grams of sulfuric acid with a specific gravity of 1.4, and 10 grams of leavening agent.

[0067] To prepare the active material paste, the dry components (lead oxide, fiber flocs, and leavening agent) were mixed in a planetary mixer for 2 minutes. Then, deionized water was added, and the resulting mixture was mixed for a further 2 minutes. Finally, sulfuric acid was added dropwise at a rate of 10 grams per minute, and the mixture was mixed for a further 3 minutes.

[0068] Next, the active material paste was applied to the electrode grid. The electrode grid was made of either 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 in a curing chamber (TPC Lunaire CEO-908-4-B-WFR Chamber). The curing process was initiated by ramping the chamber from ambient conditions to 55°C and 95% relative humidity over a period of 2 hours. Subsequently, the curing chamber was maintained at 55°C and 95% relative humidity for 48 hours to cure. Then, the curing chamber was adjusted to 60°C and 30% relative humidity over 6 hours to begin drying. Finally, the curing chamber was held at 60°C and 30% relative humidity for 20 hours to dry.

[0070] Finally, the hardened positive and negative electrode plates were alternately welded to a connecting strap to form a cell, and the lead-acid battery was assembled. Polyethylene was placed between the plates to prevent direct contact between the positive and negative electrode active materials. The lead-acid battery in Example 2 consisted of a test cell with only one positive electrode plate and two negative electrode plates. This test cell was placed in an acrylonitrile butadiene styrene (ABS) resin 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 these examples, the preparation of the battery using lead silicate as an additive in Example 1 was the same as in Example 2, but the lead silicate glass composition was mixed with the dry components that form the positive electrode (i.e., lead oxide and fiber floc). In Examples 3 and 4, lead silicate was added in amounts of 1% by mass and 2% by mass, respectively, based on the mass of lead oxide. That is, Example 3 was prepared in the same manner as Example 2, but 10 grams of lead silicate from Example 1 was added to the dry component mixture that forms the positive electrode. Similarly, Example 4 was prepared in the same manner as Example 2, but 20 grams of lead silicate from Example 1 was added to the dry component mixture that forms the positive electrode.

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

[0074] The batteries of Examples 2-4 were tested using the Maccor Series 4000 JO1370 Battery Testing Unit. The data collected during the first 20 hours of operation are shown in Table 2. The data were normalized so that Example 2 (without lead silicate) would be equivalent to 100%. [Table 2]

[0075] The raw collected data values ​​for Example 2 were normalized, and then the raw collected data values ​​for Examples 3 and 4 were normalized as percentages relative to the control values ​​to show absolute improvement or disadvantage in performance. The presented data show that, after adjustment, the variables, including the glass composition, improved compared to the control. Although the data are normalized, Examples 2-4 in Table 2 are measured in ampere-hours.

[0076] Therefore, as can be seen from Table 2, Examples 3 and 4 (with 1% and 2% by mass of lead silicate added, respectively) result in an increase in the capacity of the lead-acid battery in the early stages of its lifespan.

[0077] Furthermore, Figures 2 and 3 provide additional evidence that the addition of a glass composition containing at least 25% by mass of a single metal oxide provides an increase in the capacity of the lead-acid battery in the early stages of its life. Figure 2 graphs the discharge rate of battery 200 over 3 hours, and Figure 3 graphs the complete discharge of battery 300. As can be seen from Figure 2, batteries using 1% by mass of lead silicate 202 (Example 3) and 2% by mass of lead silicate 203 (Example 4) show an increase in early-stage capacity at a depth of discharge (DOD) of approximately 80% and a discharge rate of 3 hours compared to a lead-acid battery without lead silicate 21 (Example 2). Similarly, in Figure 3, batteries using 1% by mass of lead silicate 302 (Example 3) and 2% by mass of lead silicate 303 (Example 4) show an increase in early-stage capacity at full discharge at approximately 80% of the depth of discharge (DOD) compared to a lead-acid battery without lead silicate 301 (Example 2). In both figures, it can be seen that batteries having 1% by mass of lead silicate 202, 302 (Example 3) and 2% by mass of lead silicate 203, 303 (Example 4) result in increased capacity during the early stages of their lifespan, such as during the first 20-40 charge-discharge cycles, compared to a lead-acid battery without a glass composition containing at least 25% by mass of single metal oxide 201, 301 (Example 2).

[0078] Example 6 - Further battery preparation

[0079] Batteries were manufactured and tested in four test groups. Each battery was a BCI, type 27M, with a calcium grid alloy and embedded glass mat structure. The test groups were designated A, B, C, and D. Lead silicate was added to the pastes of test groups A, B, and C, while battery group D was manufactured without lead silicate as a control. In group A, the amount of lead silicate added was 1% by mass relative to lead oxide in the positive electrode paste. In group B, 1% by mass was added to the negative paste. In group C, 1% by mass was added to both the positive and negative pastes. Table 1 shows an overview of groups A to D. [Table 3]

[0080] The remainder of the positive paste was a mixture of lead oxide, tetrabasic lead sulfate crystals, sulfuric acid, water, and polyester fibers. The remainder of the negative paste was a mixture of lead oxide, sulfuric acid, water, polyester fibers, and a leavening agent which was a blend of carbon, lignin, and barium sulfate.

[0081] This paste was applied to an expanded lead-calcium alloy grid. The paste had a density of approximately 4.47 grams per cubic centimeter, contained approximately 11% moisture, and had a penetration depth of 2.9 millimeters. This was within the range of the manufacturing standard specifications and consistent with previous rheological experiments, demonstrating that the properties of the paste were not affected by lead silicate at this loading rate. After the grid was attached, embedded glass mat paper was rolled onto each side of the plate. Subsequently, before curing, it was flash-dried through an oven to reduce the moisture content to approximately 10%. The plate was cured at a relative humidity of over 95% and a temperature of 85°C for 9 hours, then held for a further 3 hours to dry according to the manufacturing specifications. The cured positive electrode plate weighed approximately 150g, containing 50g of grid and 100g of cured material, while the cured negative electrode plate weighed 120g, containing 25g of grid and 95g of cured material.

[0082] After curing, this plate was assembled into a 27M type battery. A polyethylene separator sleeve was placed on the negative electrode plate, and the battery elements were stacked at a ratio of 8 positive electrodes and 7 negative electrodes per cell. The rest of the battery assembly was then performed according to the manufacturer's standard procedure. Finally, 1.4 grams of sulfuric acid per milliliter was added to the fully assembled battery, and the battery was charged to capacity according to the manufacturer's specifications.

[0083] Evaluation of the battery in Example 7 - Example 6

[0084] Prior to the electrical testing, the following measurements were taken for each battery: average mass of 23 kg; average open-circuit voltage of 12.75 volts; and specific gravity of each battery was recorded. The average specific gravity was approximately 1.28 grams of sulfuric acid per milliliter of electrolyte. There were no significant differences in battery mass among the four groups.

[0085] Eight batteries were selected for testing, two from each group. The battery with the smallest relative specific gravity difference between cells was chosen. Holes were drilled in the first and third cells from the positive electrode, and the specific gravity was measured just below the surface of the electrolyte, as close to the bottom as possible (approximately 5.5 inches). This was the approximate length of the sampling tube of the digital hydrometer used for the measurement. Prior to the results mentioned in Figure 2, pre-capacity and cold-crank tests were performed. The pre-capacity profile involved discharging to less than 10.5 volts at 25 amps, then charging to more than 15.3 volts at 20 amps, and then charging to 18 volts at 5 amps for 7 hours or 18 volts. The cold-cranking profile involved discharging to 6 volts at 0°C with 800 amps. Then, it was charged to 115 percent and boosted at 15 amp-hours. In the ampere-hour tests for C5, C10, C20, and C100 batteries, they were discharged at the current determined by the spare capacity data for each battery, resulting in stratified results of approximately 17A, 9.7A, 5.25A, and 1A, respectively.

[0086] Table 4 shows the measured values ​​of the specific gravity difference between the upper and lower parts of the cell. Measurements were taken after charging and before the next discharge. A specific gravity difference of 0.015 (15 points) or more between the upper and lower parts of the cell was considered to indicate that stratification had occurred in the battery. [Table 4]

[0087] Stratification is minimal during discharge, but the difference in specific gravity between the top and bottom of the battery is greatest during charging. Overcharging is one method of electrolyte mixing. Table 4 shows data on specific gravity measurements before discharge. In the control batteries of Group D, acid stratification was observed after discharge of C20 and C100. In the charging profile of 115% charge recovery + 15Ah boost charge, the acid could not be sufficiently mixed in these two cases. From these results, the reduction of acid stratification is as follows: addition of both positive electrode active material (PAM) and negative electrode active material (NAM) > NAM only > PAM only > control.

[0088] One or more aspects of the present disclosure are described herein. A first aspect of the present disclosure may include a method for forming a precursor of an active material for electrodes of a lead-acid battery, comprising forming an active material paste by combining at least water, an acid, a glass composition comprising at least 25% by mass of a single metal oxide, and lead oxide, wherein the glass composition is granular, the lead oxide is granular, the metal oxide is selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide, and curing the active material paste to form a precursor of an active material for electrodes of a lead-acid battery.

[0089] A second aspect of this disclosure is a metal silicate in which the glass composition has a composition comprising 40% to 99% by mass of PbO and 1.0% to 60% by mass of SiO2, and may include the first aspect.

[0090] A third aspect of this disclosure may include the first aspect, wherein the glass composition comprises 40% to 99% by mass of PbO, 1.0% to 60% by mass of SiO2, and 0.1% to 10% by mass of Al2O3.

[0091] A fourth aspect of this disclosure may include any one of the first to third aspects, wherein the acid includes sulfuric acid.

[0092] A fifth aspect of this disclosure is one of the first to fourth aspects, wherein the mass ratio of the glass composition to lead oxide in the active material paste is in the range of 1:200 to 1:3.33.

[0093] A sixth aspect of this disclosure is a fourth aspect, wherein the mass ratio of sulfuric acid to lead oxide in the active material paste is in the range of 1:100 to 1:10.

[0094] A seventh aspect of the present disclosure further comprises combining fibers, water, acid, a glass composition, and lead oxide to form an active material paste, and may include any one of the first to sixth aspects.

[0095] An eighth aspect of the present disclosure further comprises bringing the active material paste into contact with an electrode grid before the active material paste hardens, and may include any one of the first to seventh aspects.

[0096] A ninth aspect of the present disclosure is that the glass composition comprises at least 25% by mass of barium oxide and may include any one of the first to eighth embodiments.

[0097] A tenth aspect of this disclosure is that the glass composition comprises at least 25% by mass of lead oxide and may include any one of the first to ninth embodiments.

[0098] An eleventh aspect of the present disclosure may include any one of the first to tenth aspects, wherein the glass composition comprises at least 25% by mass of zinc oxide.

[0099] A twelfth aspect of the present disclosure may include any one of the first to eleventh aspects, wherein the glass composition comprises at least 25% by mass of antimony oxide.

[0100] A thirteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein the glass composition comprises at least 25% by mass of tin oxide.

[0101] A 14th aspect of the present disclosure may include a precursor for an active material of a lead-acid battery, the precursor being formed by a step of forming an active material paste by a method comprising combining at least water, an acid, a glass composition comprising at least 25% by mass of a single metal oxide, and lead oxide, and curing the active material paste to form an active material precursor for electrodes of a lead-acid battery, wherein the glass composition is granular, the lead oxide is granular, and the metal oxide is selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide.

[0102] A fifteenth aspect of the present disclosure is a metal silicate in which the glass composition comprises 40% to 99% by mass of PbO, 1.0% to 60% by mass of SiO2, and less than 10% by mass of Al2O3, and may include the fourteenth aspect.

[0103] A sixteenth aspect of this disclosure may include either the fourteenth or fifteenth aspect, wherein the acid includes sulfuric acid.

[0104] A 17th aspect of this disclosure is one in which the mass ratio of the glass composition to lead oxide in the active material paste is in the range of 1:200 to 1:3.33, and may include any one of the 14th to 16th aspects.

[0105] An eighteenth aspect of this disclosure is one in which the mass ratio of sulfuric acid to lead oxide in the active material paste is in the range of 1:100 to 1:10, and may include the seventeenth aspect.

[0106] A 19th aspect of the present disclosure may include a lead-acid battery, the lead-acid battery comprising an electrolyte, at least one negative electrode plate, and at least one positive electrode plate, wherein at least one or both of the negative electrode plate and at least one positive electrode plate contain an active material formed from an active material precursor, the active material precursor being formed by a process comprising forming an active material paste by a method including combining at least water, an acid, a glass composition containing at least 25% by mass of a single metal oxide, and lead oxide, and curing the active material paste to form an active material precursor for the electrodes of the lead-acid battery, wherein the glass composition is granular, the lead oxide is granular, and the metal oxide is selected from the group consisting of barium oxide, lead oxide, zinc oxide, tin oxide, or antimony oxide.

[0107] A 20th aspect of this disclosure may include the 19th aspect, wherein the electrolyte solution comprises water and sulfuric acid.

[0108] A 21st aspect of the present disclosure is a metal silicate in which the glass composition comprises 40% to 99% by mass of PbO and 1.0% to 60% by mass of SiO2, and may include either the 19th or 20th aspect.

[0109] Please note that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purpose of defining the Art, this term is introduced into the claims as an open-ended transitional phrase used to introduce a description of a set of structural characteristics, and should be interpreted in a similar manner to the more commonly used open-ended preamble term “comprising.”

[0110] Any two quantitative values ​​assigned to a particular characteristic may constitute a range for that characteristic, and it should be understood that all combinations of ranges formed from all stated quantitative values ​​for a given characteristic are contemplated in this disclosure.

[0111] While the subject matter of this disclosure has been described in detail and with reference to specific embodiments, it should be noted that the various details described herein should not be taken to suggest that these details relate to essential components of the various embodiments described herein, even if certain elements are illustrated in each of the drawings accompanying this description. Rather, the claims attached herein should be considered to represent the breadth of this disclosure and the corresponding scope of the various embodiments described herein. Furthermore, it will be apparent that modifications and variations are possible without departing from the scope of the attached claims.

Claims

1. A method for forming a precursor for the active material of electrodes in a lead-acid battery, At least, water, acid, and SiO ２ The process includes a step of forming an active material paste, which involves mixing a glass composition containing at least 70% by mass of a single metal oxide with lead oxide, The process includes curing the active material paste to form the precursor of the active material for the electrodes of the lead-acid battery, The glass composition is granular, and the lead oxide is granular. The method wherein the metal oxide is lead oxide.

2. The glass composition comprises 70% to 99% by mass of PbO and 1.0% to 30% by mass of SiO ２ The method according to claim 1, wherein the metal silicate is a composition comprising the following.

3. The glass composition comprises 70% to 99% by mass of PbO and 1.0% to 29.9% by mass of SiO ２ And, 0.1 mass% to 10 mass% Al ２ O ３ The method according to claim 1, comprising the following:

4. The method according to claim 1, wherein the acid includes sulfuric acid.

5. The method according to claim 4, wherein the mass ratio of sulfuric acid to lead oxide in the active material paste is in the range of 1:100 to 1:

10.

6. The method according to claim 1, wherein the mass ratio of the glass composition to lead oxide in the active material paste is in the range of 1:200 to 1:3.

33.

7. The method according to claim 1, wherein the step of forming the active material paste further comprises mixing fibers, water, acid, a glass composition, and lead oxide.

8. The method according to claim 1, further comprising the step of bringing the active material paste into contact with an electrode grid before the step of curing the active material paste.

9. A precursor for an active material of a lead-acid battery, wherein the precursor is formed by the method described in any one of claims 1 to 8.

10. It is a lead-acid battery, Electrolyte solution and, At least one negative electrode plate, It comprises at least one positive electrode plate, At least one of the negative electrode plate and at least one of the positive electrode plate, or both, contain an active material formed from an active material precursor. A lead-acid battery in which the precursor of the active material is formed by the method described in any one of claims 1 to 8.

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