Patent Application
20240006587
The present invention relates to lead electrode plate structure and a method for making thereof, especially related to using non-metallic material to make an electrode plate for manufacturing a lead-acid battery. The present invention also relates to an art for preventing lead-acid battery from lead (II) sulfate crystal growth piercing and enhancing the battery formation efficiency
Regarding conventional lead-acid battery manufacturing, the aqueous sulfuric acid solution immersing the electrode plate stack is prone to have chemical reaction with the electrode plate within the cassette. The chemical reaction leads to that sulfuric acid concentration in central area of the electrode plate is lower than that in the surrounding area, which eventually results in issues of pure hydration in central area of the electrode plate. Pure hydration in central area of the electrode plate makes it easier for lead sulfate to dissolve into the aqueous sulfuric acid, and crystalize on the electrode plate to grow lead dendrite. The lead dendrites gradually bridge between the electrode plates and eventually cause short circuit of the battery.
Electrode plate stack prepared by stacking conventional electrode plates creates insufficient porosity for air permeability from one plate to another. Taking continuous lead paste coating process for example, the electrode plate surface is covered by a lead paste paper so as to prevent lead paste coated upon the electrode plate from sticking to other battery components such as another electrode plate or a separator. However, currently-used lead paste paper for continuous lead paste coating process could not provide sufficient air permeability. When aqueous sulfuric acid solution is poured into the lead-acid battery, gas and heat produced in chemical reaction between the aqueous sulfuric acid solution and the electrode plate cannot dissipate rapidly through the conventional lead paste paper. In addition, in high capacity lead-acid battery, such as lead-acid battery having capacity above 50 Ah or 100 Ah, the size of their electrode plates are often larger than those in a conventional lead-acid battery. Larger-sized electrode plates render it difficult for the aqueous sulfuric acid solution in central area of the electrode plate to reach an equilibrium in terms of concentration with the aqueous sulfuric acid solution in the surrounding area through convective diffusion. During charge and discharge process, pure hydration tends to be observed in central area of the larger-sized electrode plate such that lead sulfate is dissolved and attached to the lead paste paper or the separator. The attached lead sulfate attracts more lead microparticles to grow into lead dendrite. The continuously growing lead dendrite pierces through the separator and bridge between positive and negative electrode plates, causing battery short circuit.
Confronted with the aforementioned technological issues in the prior arts, there is an urgent need to develop an electrode plate capable of reducing lead sulfate crystallization and suppressing lead dendrite growth in order to prolong lifespan and increase operational efficiency of the lead-acid battery. In one aspect, the present invention discloses a lead-acid battery electrode plate for preventing lead sulfate dendrite growth and enhancing batter formation efficiency, comprising: a electricity collector layer provided to be an electricity channel; a first air-permeable layer comprising a non-metallic sheet material and provided on one side of the electricity collector layer; a second air-permeable layer comprising a non-metallic sheet material and provided on other side of the electricity collector layer in a corresponding manner to the first air-permeable layer, wherein the non-metallic sheet material has a porous structure to be air-permeable channels, and the first air-permeable layer is the same to or different from the second air-permeable layer.
Preferably, the porous structure comprises one or more interwoven layers, and the interwoven layers are prepared by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle.
Preferably, the porous structure comprises a electrical conductive material, a corrosion-resistant material or a combination thereof, wherein the electrical conductive material comprises one or more materials selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material comprises one or more materials selected from a group consisting of polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
Preferably, wherein the porous structure is a fabric braid comprising a fabric braid woven from long electrical conductive fiber materials, a fabric braid woven from long electrical conductive fiber materials and short electrical conductive fiber materials, a fabric braid woven from long corrosion-resistant fiber materials, a fabric braid woven from long corrosion-resistant fiber materials and short corrosion-resistant fiber materials, a fabric braid woven from long electrical conductive fiber materials and long corrosion-resistant fiber materials, or a fabric braid woven from long corrosion-resistant fiber materials, short corrosion-resistant fiber materials, and long corrosion-resistant fiber materials, short corrosion-resistant fiber materials.
Preferably, the porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof, wherein the electrical conductive materials is selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material is glass fiber.
In another aspect, the present invention discloses a lead-acid battery comprising: a seal case; an electrode plate stack, sealed in the seal case, comprising: a separator; an positive electrode plate comprising the aforementioned lead-acid battery electrode plate, provided on one side of the separator; a negative electrode plate comprising the aforementioned lead-acid battery electrode plate, provided on the other side of the separator in a corresponding manner to the positive electrode plate; and an electrolyte solution, sealed in the seal case and immersing the electrode plate stack, dissolving acidic electrolyte.
In one another aspect, the present invention discloses a method for making an lead-acid battery electrode plate comprising: placing one first non-metallic sheet material and one second non-metallic sheet material on two sides of the electricity collector layer in a respective manner so as to obtain the lead-acid battery electrode plate, wherein the first non-metallic sheet material and the second non-metallic sheet material have porous structures to be air-permeable channels of a first air-permeable layer and a second air-permeable layer, and the first air-permeable layer is the same as or different from the second air-permeable layer.
Preferably, wherein the porous structure comprises one or more interwoven layers, the interwoven layers are made by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle.
Preferably, wherein before obtaining the lead-acid battery electrode plate, the method further comprising exerting a pressure on the lead-acid battery electrode plate so as to laminate the electricity collector layer, the first non-metallic sheet material and the second non-metallic sheet material in a more intense manner.
Preferably, the method comprises using a roller to exert the pressure on the first non-metallic sheet material—the electricity collector layer—the second non-metallic sheet material composite so as to obtain the lead-acid battery electrode plate.
Preferably, wherein the porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof, wherein the electrical conductive materials comprises one or more materials selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material comprises one or more materials selected from a group consisting of polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber.
Preferably, he porous structure comprises a electrical conductive materials, a corrosion-resistant material or a combination thereof, wherein the electrical conductive materials is selected from a group consisting of electrical conductive polymers, nanocarbon, graphite and graphene; the corrosion-resistant material is glass fiber.
In yet one another aspect, the present invention discloses a lead-acid battery comprising: a seal case; an electrode plate stack, sealed in the seal case, comprising: a separator; an positive electrode plate comprising a lead-acid battery electrode plate made by the aforementioned method, provided on one side of the separator; a negative electrode plate comprising a lead-acid battery electrode plate made by the aforementioned method, provided on the other side of the separator in a corresponding manner to the positive electrode plate; and an electrolyte solution, sealed in the seal case and immersing the electrode plate stack, dissolving acidic electrolyte.
The lead-acid electrode plate disclosed herein enhances air permeability of the lead-acid electrode plate itself. Gases which is produced during electrochemical reaction are more efficiently ventilated. Vulcanization on the lead-acid electrode plate is reduced so that short circuit of the battery due to lead dendrite growth is also suppressed. Meanwhile, electrical conductive materials are added to the non-metallic sheet materials, which benefits conductivity, electric capacity and formation efficiency. The corrosion-resistant materials ameliorates pure hydration issues in the center area of the electrode plate. Overall, the lead-acid battery can be more quickly put into subsequent applications, and battery lifespan is also significantly prolonged.
The following is a description of the structure and usage of various components of the present invention through several exemplary implementations, aiming to provide a detailed explanation of the features of the present invention. However, these embodiments are only intended to illustrate the core essence of the present invention and should not be construed as limiting the implementation of the present invention.
Please refer to
Normally when a lead-acid battery is in use, vulcanization tends to be observed in the surface of a lead-acid battery electrode plate, which results from electrochemical reaction between the electrolyte solution and the lead-acid battery electrode plate, and such a situation is hard to avoid. Major reasons of surface vulcanization include large current discharge, deep discharge, not-timely charge, frequently charge or charge within overly short period. In the present invention, enhancement of air permeability in the lead-acid electrode plate (100) not only increases ventilation of hydrogen and oxygen produced during charge and discharge, but also prevents battery damages caused by swelling pressure from the battery interiority. In addition, surface vulcanization of the lead-acid battery electrode plate (100) can also be reduced, which suppresses lead dendrite growth that penetrates the adjacent separator.
In various embodiments, as shown in
In various embodiments, as shown in
In other embodiments, as shown in
To improve ventilation property of the electrode plate during an electrochemical reaction, the air-permeable layer facing the separator (S) requires higher air permeability. Preferably, the second air-permeable layer (3) having higher air permeability faces the separator (S), wherein the air permeability of the second air-permeable layer (3) is higher than the air permeability of the first air-permeable layer (2). In particular, the air permeability is determined by averaged concentration of the electrolyte solution before and after the lead-acid battery electrode plate (100) is immersed in the electrolyte solution. When difference of averaged electrolyte concentrations nearby central area of the lead-acid electrode plate (100) before and after electrolyte solution immersion is smaller, it indicates that the air-permeable layers (1, 2) have higher porosity. Such improvement of ventilation addresses pure hydration issues in central area of the plate. On the contrary, when difference of averaged electrolyte concentrations nearby central area of the lead-acid electrode plate (100) before and after electrolyte solution immersion is larger, it indicates that the air-permeable layers (1, 2) have less porosity, which is unfavorable for ventilation and leads to pure hydration issues in central area of the electrode plate. Eventually, lead dendrite tends to grow on the electrode plate during an electrochemical reaction.
To give the lead-acid battery electrode plate (100) the air permeability as mentioned hereinabove, in various embodiments, the porous structure is a fiber braid (), comprising one or more interwoven layers. The interwoven layers are prepared by interweaving a plurality of latitudinal threads and a plurality of longitudinal threads, wherein an intersection angle formed between any one of the latitudinal threads intersecting with any one of the longitudinal threads is an acute angle or an obtuse angle. In particular, the acute angle measures between 0 to 90 degrees, but not 0 degree. The obtuse angle measures between 90 to 180 degrees, but not 90 degrees or 180 degrees. Preferably, the latitudinal threads and the longitudinal threads can be long fibers, short fibers or any combination thereof. More preferably, a plurality of pores of various sizes are formed in the interwoven layers by random weaving the long fibers and the short fibers. The pores connects to each other and forms multiple air-permeable channels when the interwoven layers are stacked together to form the porous structure. The air-permeable channels enhance the air permeability of the porous structure. On the other hand, to avoid adverse effects on the air permeability of the porous structure, during formation of the porous structure, no crosslinking agent or binding agent is added because such additives would fill in the channels so that the air permeability is reduced.
In some embodiments, thickness of the first air-permeable layer (2) ranges from to 0.4 mm, and thickness of the second air-permeable layer (3) ranges from 0.1 to 0.4 mm; preferably, thickness of the first air-permeable layer (2) ranges from 0.2 to 0.3 mm, and thickness of the second air-permeable layer (3) ranges from 0.2 to 0.3 mm.
In the above embodiments, to improve formation efficiency of the lead-acid battery, the non-metallic sheet material is made of electrical conductive materials having high electrical conductivity. The electrical conductive materials can be exemplified by electrical conductive polymers, activated carbon, nanocarbon, graphite or graphene. The electrical conductive polymers can be polyacetylene-based polymers, polyparastyrene-based polymers, polyaniline, polypyrrol-based polymers, polyfluorene-based polymers, polyparaphenylene sulfide, polybenzazole-based polymers, polycarbazole-based polymers, polyazulene-based polymers, polynaphthyl polymers, polythiophene-based polymers, polythiophene-vinylidene polymers, or derivatives of any one thereof. In preferred embodiments, the electrical conductive materials are manufactured into electrical conductive fiber materials such as activated carbon fibers, nanocarbon fibers, graphite fibers or graphene fibers, and the interwoven layers are prepared by interweaving the electrical conductive fiber materials as the longitudinal threads and the latitudinal threads. In more preferred embodiments, the electrical conductive materials are manufactured into electrical conductive cloth materials such as carbon fiber cloth, carbon nanotube fiber cloth, activated carbon cloth and graphene fiber cloth.
The “formation efficiency” is for evaluation of activation efficiency of a lead-acid battery in initial charge and discharge. During the initial electrical charge of the lead-acid battery, a passivated film is formed on the surface of either the positive electrode or the negative electrode, whereas the positive electrode having a thinner passivated film is not further discussed. The passivated film is formed by consuming lead ions of the electrode plate when a chemical reaction is triggered between the electrolyte solution and the electrode plate. For example, lead sulfate is produced and forms a thin film blocking electrons and electrolyte solution. Formation efficiency is critical for lead-acid battery performance. Generally speaking, the lead-acid battery is charged using constant current and constant voltage methods, such as charging at rates of 0.1 C, 0.2 C or 0.3 C, to evaluate whether the voltage consistency of lead-acid battery meets desired requirement during constant current charging. During formation process, the lead-acid battery produces gas in an electrochemical reaction. While at a particular voltage, a passivated film forms on the surface of negative electrode so that reductive reaction of the electrolyte solution is suppressed, and gas production also is decreased dramatically.
In order to ventilate the gas produced in the aforementioned chemical reaction from surfaces of the electrode plates, the non-metallic sheet material is made by interweaving non-electrical conductive corrosion-resistant materials and the electrical conductive materials. The corrosion-resistant materials can be exemplified by polypropylene, polyethylene, polyester, nylon, aramid, polyvinyl chloride, acrylic, viscose, glass, spandex, polyacrylate, or polyimide; preferably, the corrosion-resistant materials are manufactured into corrosion-resistant fiber materials such as polypropylene fiber, polyethylene fiber, polyester fiber, nylon fiber, aramid fiber, polyvinyl chloride fiber, acrylic fiber, viscose fiber, glass fiber, spandex fiber, carbon fiber, polyacrylate fiber and polyimide fiber. The corrosion-resistant fiber materials are subsequently interwoven as the longitudinal threads and the latitudinal threads into the interwoven layers, or the corrosion-resistant fiber materials and the electrical conductive fiber materials are taken as the longitudinal fibers and the latitudinal fibers, respectively, and interwoven into the interwoven layers, but not limited to this.
Please refer to
In some embodiments, the non-metallic sheet material comprises 1.00 to the electrical conductive materials and 0.10 to 2.00 wt % the corrosion-resistant materials. Preferably, the non-metallic sheet material comprises 1.50 to 5.00 wt % the electrical conductive materials and 0.20 to 1.50 wt % the corrosion-resistant materials. More preferably, the non-metallic sheet material comprises 1.80 to 4.70 wt % the electrical conductive materials and 0.25 to 1.25 wt % the corrosion-resistant materials.
In another aspect, as shown in
In some embodiments, the electrolyte (E) is an aqueous acidic solution, generally an aqueous sulfuric acid solution, and a 30 to 40 wt % aqueous sulfuric acid solution is preferred. Please refer to
In some embodiments, preferably, any one of the positive electrode plates (C, C′) is enclosed by the separators (S) so that the positive electrode (C, C′) is isolated from the negative plate (A, A′, A″) adjacent the positive electrode (C, C′).
To be specific, the lead-acid battery (200) provided in the present invention demonstrates lower pure hydration in central area of the electrode plate than that of a conventional lead-acid battery during a manufacturing process. In other words, the disparity in electrolyte concentration between central area and surrounding area of the lead-acid electrode plate (100) is smaller in comparison with that of a conventional lead-acid battery. The “central area” is geometric center of the electrolyte-contacting surface of the electrode plate, and “surrounding area” is the outermost perimeter defining the electrode plate. Comprehensibly, the shape of the electrode plate is not limited, and it can be a square, a round or any type of polygon, while the central area can be just defined in accordance to the definition of a polygonal geometric center in geometry. As shown in
In some embodiments, the separator (S) comprises a material selected from a group consisting of absorbent glass mat, polyvinyl chloride, polyolefin and non-woven fiber glass mat. In preferred embodiments, the separator (S) is made of absorbent glass mat.
Please refer to
In yet another aspect, the present invention provides a method for making an lead-acid battery electrode plate, as shown in
Step S1: placing one first non-metallic sheet material (NM1) and one second non-metallic sheet material (NM2) on two sides of the electricity collector layer (1) in a respective manner so as to obtain the lead-acid battery electrode plate (100), wherein the first non-metallic sheet material (NM1) and the second non-metallic sheet material (NM2) have porous structures to be air-permeable channels of a first air-permeable layer (2) and a second air-permeable layer (3), and the first air-permeable layer (2) is the same as or different from the second air-permeable layer (3).
In some embodiments, please continue to refer to
Step S1-2: exerting a pressure on the lead-acid battery electrode plate (100) so as to laminate the electricity collector layer (1), the first non-metallic sheet material (NM1) and the second non-metallic sheet material (NM2) in a more compact manner, wherein the pressurizing procedure can be squeezing, rolling, or compressing by a compressor.
Please further refer to
Moreover, the roller system (300) further comprises a material supplying device (34) for allocating a lead paste (P) to the lead grid (L). The material supplying device (34) pours the lead paste (P) into each grid opening (0), and the lead paste (P) penetrates the lead grid (L) so as to envelope both sides of the lead grid (L). In this example, the raw electrode plate (RS) comprises, sequentially top to bottom, the first non-metallic sheet material (NM1), the lead grid (L)—the lead paste (P), the second non-metallic sheet material (NM2), and compactly pressed by the second rolling unit (322) on the delivery belt (331) upon the second roller (333) so as to form the electrode plate strip (RSs). Subsequently, the electrode plate strip (RSs) is cut into an individual lead-acid battery electrode plate (100), and dried, stored, and solidified so as for assembling a lead-acid battery.
In some other embodiments, please continue on
Preparing an unformed electrode plate sizing 23.9 cm in length, 16.2 cm in width, and 0.3 cm in thickness, and 2 pieces of non-metallic sheet materials having 2 cm thickness. Placing the unformed electrode plate between the 2 pieces of non-metallic sheet materials to obtain an electrode plate having air-permeable layers, wherein the non-metallic materials comprises carbon fibers and ceramic fibers.
Preparing an unformed electrode plate sizing 23.9 cm in length, 16.2 cm in width, and 0.3 cm in thickness.
Electrode plates in the embodiment 1 and the comparative example 1 were applied as the positive electrode plate (C) and the negative electrode plate (A). The positive electrode plate (C) was enclosed by the separator (S), and alternatively stacked with the negative electrode plate (A) into an electrode plate stack. The electrode plate stack was placed into a battery seal case to form a lead-acid battery. The seal case was filled with aqueous sulfuric acid solution at concentration of 1.28M, and the electrode plate stack was immersed in the aqueous sulfuric acid solution for 40 minutes. Temperature of the aqueous sulfuric acid solution was measured around 40° C. Probe of a densimeter reached the central area of the positive electrode plate (C) and the negative electrode plate (A), respectively, and reached surrounding area neighboring the electrode plate stack periphery fin order to measure concentrations of aqueous sulfuric acid solution. Pure hydration status could be determined through observing aqueous sulfuric acid concentration variations in central area of the electrode plate.
As shown in TABLE 1, compared with the initial concentration of aqueous sulfuric acid solution in central area of the electrode plate, in both cases where embodiment 1 was applied as the positive electrode plate or the negative electrode plate, the percentage decrease was lower (5.8% and 3.3%, respectively) in comparison with to the percentage decrease (7.1% and 4.0%, respectively) observed in comparative example 1.
Moreover, please refer to TABLE 2, compared with the concentration of aqueous sulfuric acid solution in surrounding area of the electrode plate stack, in both cases where embodiment 1 was applied as the positive electrode plate or the negative electrode plate, the concentration ratio of central area to surrounding area was lower (1.027 and 1.000, respectively) in comparison with the concentration ratio of central area to surrounding area (1.034 and 1.019, respectively) observed in comparative example 1. The disparity in concentrations of the aqueous sulfuric acid solution between the central area and the surrounding area of the embodiment 1 was smaller. This demonstrates that the addition of non-metallic sheet materials to the embodiment 1 helped to more efficiently maintain the concentration of the aqueous sulfuric acid solution in central area of the electrode plate. This improvement addresses the pure hydration issues in central area of the electrode plate.
Electrode plates prepared in embodiment 1 and comparative example 1 were applied as positive electrode plates or negative electrode plates for assembling lead-acid batteries. The lead-acid batteries were charged at a constant current of 0.17 C and discharged at a constant current of 0.25 C repeatedly for 3 times. Subsequently, surfaces of the electrode plates were observed whether there was lead sulfate dendrite growth or not. As shown in
The lead-acid electrode plate provided in the present invention demonstrates improvement of its air permeability by substituting conventional paste paper for the non-metallic sheet materials. During charge and discharge of the battery, the lead-acid electrode plate could more efficiently ventilate gases produced in electrochemical reaction in comparison with the electrode plate using conventional paste paper. Therefore, electrolyte solution could move more rapidly from surrounding area to central area of the lead-acid electrode plate, and slows down concentration decrease in the central area. Such improvement addresses pure hydration issues in central area of the lead-acid electrode plate. Meanwhile, battery damage owing to interior swelling pressure could be avoided. Surface vulcanization of the lead-acid battery can also be minimized to prevent battery short circuit resulting from lead dendrite.
The lead-acid electrode plate provided in the present invention exhibits superior characteristics compared to conventional paste paper. It not only enables efficient ventilation but also demonstrates excellent electrical conductivity and increased electric capacity. This is achieved by incorporating electrical conductive materials into the non-metallic sheet material. Along with increased electrical conductivity, formation efficiency of the lead-acid battery is also improved so that the lead-acid battery can be put into subsequent application more quickly. Furthermore, the incorporation of electrical conductive materials into the non-metallic sheet material helps reduce surface vulcanization. This reduction allows for the maintenance of a constant working area even after multiple cycles of charge and discharge. As a result, the battery exhibits improved long-term working efficiency with less decline over time, and the lifespan of the battery is also significantly prolonged.
Fibers of the non-metallic sheet materials are not interwoven in a perpendicular manner, which not only creates more channels for electrolyte solution flow, but also addresses pure hydration issues in central area of the lead-acid electrode plate by incorporation of the non-electrical conductive fiber materials to the electrical conductive fiber materials.
This application claims the benefit of U.S. Provisional Application Ser. No. 63/356,490, filed Jun. 29, 2022.
| Number | Date | Country | |
|---|---|---|---|
| 63356490 | Jun 2022 | US |
