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In order to prevent corrosion of the positive electrode grid, a multi-element low antimony alloy has been developed. The corrosion resistance of this multi-element alloy has been significantly improved. The negative electrode grid adopts lead plated copper mesh. The ratio of the weight of the copper grating to the active material is 1:3, and the specific energy of the storage tank is significantly improved. Moreover, due to the good electrical performance and strong charging acceptance ability of the copper plate grid negative electrode, the battery's charge and discharge cycle life is extended. Adding additives to the positive and negative active substances can improve their utilization efficiency and extend their service life. Comprehensive anti short circuit measures have been taken to prevent lead wool short circuits. We have adopted high-performance boards and a series of new assembly processes.

Introduction to the Development of Lead Acid Batteries

Lead acid batteries were first made by Gaston Prandt in 1860 and have a history of over 140 years. For over a hundred years, with the development of science and technology, the process, structure, production mechanization, and automation level of lead-acid batteries have been continuously improved, and their performance has been continuously enhanced. Due to its excellent performance price ratio, lead-acid batteries still rank first in terms of production and application among various chemical power sources to this day. Its applications mainly include power, starting, emergency, and working power sources, and its users include vehicles, ships, airplanes, telecommunications systems, computers, instruments, and other equipment and facilities. Especially in automotive batteries and industrial batteries, lead-acid batteries account for more than 90% of the market share and have an absolute advantage. The original Valta fuel cell first appeared in 1800. In 1801, Gottelot had already observed the so-called 'secondary current', which means that after charging, a current in the opposite direction to the charging current can be obtained. Dela Zaowei studied the use of Pb02 as a positive electrode in sulfuric acid solution for primary batteries from 1836 to 1843. The various electrode forms and manufacturing processes of lead-acid batteries were gradually determined over the course of half a century from 1860 to 1910. The earliest to appear was the formation type electrode plate. In 1881, Foucault first proposed the paste coated electrode plate. Xie Lang was the first to use Pb.sb alloy to cast grids, with the aim of improving the fluidity of liquid alloys and their hardness in the solid state. In 1924, R himself, Shimadzu, invented the ball mill and used ball milling powder instead of red and yellow lead powder as the active material for batteries. The use of lignin as a negative electrode active material additive effectively prevents the coarsening of lead sulfate crystals and extends the life of the battery. In the 1920s, microporous rubber separators appeared, and in the 1940s, resin paper separators gradually replaced wooden separators. From the 1950s to the 1960s, there were several significant advances in the manufacturing process of lead-acid batteries: using plastic instead of hard rubber to manufacture battery slots and covers; Adopting thin electrode plates and improving grid design; Wall welding technology applied to starting batteries; Low antimony or antimony free alloy casting grids are commonly used; Improve the utilization rate of active substances during short-term discharge; Manufacturing process of dry charged batteries. After the 1970s, countries around the world vigorously developed maintenance free and sealed lead-acid batteries. In terms of basic theory, the achievements and methods of physics, especially electronics, were widely adopted, including potentiometers, scanning ammeters, scanning electron microscopes, X-ray and neutron diffraction, nuclear magnetic resonance and electron spectroscopy, as well as rotating disk electrodes and computer technology. The research focus has shifted from thermodynamics to electrode process kinetics.

The main manufacturers of lead-acid batteries are distributed in several developed countries including the United States, Europe (such as the United Kingdom, Germany, France, etc.), and Japan, with their total production accounting for about 70% of the world's total production. The United States has EXIDE Technologies, the world's largest lead-acid battery manufacturer with annual global sales of $2.8 billion, as well as other very large lead-acid battery manufacturers such as JOHNSON, CON, DEKA, DELPHI, and others. The production value of lead-acid batteries in the United States accounts for about 20% of the world's total, but in recent years, with changes in technology, labor costs, and other factors, some lead-acid battery companies have experienced a decline in their operations. The production of lead-acid batteries is shifting to countries and regions with low labor costs, such as China, India, and Southeast Asia. Europe has many large lead-acid battery manufacturers, such as CHLORIDE, HOPPECKE, F1AMM, DETA, HAWKER, etc. Lead acid batteries in Europe hold an important position globally, with well-established technology advanced lead-acid battery manufacturers such as Sunac (now a subsidiary of EXIDE). In 2001, the production of starting lead-acid batteries in Europe was 48.1 million units, and it is expected to be 49.1 million units in 2002. In 2005, it will reach 51.8 million units. In terms of industrial batteries, in 2000, there were 130000 liquid rich backup batteries, 110000 sealed batteries with less than 24Ah, and 430000 sealed batteries with more than 24Ah. The main manufacturers of lead-acid batteries in Japan include Yuasa Battery Company, Panasonic Battery Company, Koga Battery Company, Shin Kobe Electric Company, and Japan Battery (GS) Company. According to relevant statistics, the output value of lead-acid batteries in Japan was about 1.16 billion US dollars in 2002. Among lead-acid batteries, automotive starter batteries accounted for 55.7%, industrial batteries (fixed lead-acid batteries) accounted for 6.7%, small lead-acid batteries accounted for 8.0%, and others accounted for 29.7%. Since the 1990s, the proportion of lead-acid batteries in the total output value of secondary batteries has remained at around 20%, and has increased in recent years.

In recent years, the performance of lead-acid batteries in China has greatly improved, with significant increases in both weight to energy ratio and volume to energy ratio. The development of low maintenance and maintenance free, valve regulated sealed lead-acid batteries is rapid.

Structure, composition, and classification of lead-acid batteries

The electrochemical expression of lead-acid batteries is: (1) PbIH2SO · IPb02 (+).

The main structure of lead-acid batteries includes a positive electrode, a negative electrode, a separator, sulfuric acid electrolyte, a battery compartment, and a cover. The positive and negative poles are welded together to form a pole group, and in high-capacity batteries, they are led out from the busbar to form pole columns. The electrolyte used in lead-acid batteries is a certain concentration of sulfuric acid electrolyte. The function of a rain barrier is to separate the positive and negative electrodes. It is an electrical insulator (such as rubber, plastic, fiberglass, etc.), resistant to sulfuric acid corrosion, oxidation, and has sufficient porosity and pore size to allow electrolyte and ions to freely pass through. The tank body is also an electrical insulator, with a wide range of acid and temperature resistance, high mechanical strength, and generally made of hard rubber or plastic.

Analysis of cycle life of lead-acid batteries

1.2.1 Positive electrode active material

The positive electrode active material is lead dioxide. The crystal forms of Pb02 include d-Pb02 and 0-Pb02. In sulfuric acid solution,

The reaction of Pb02 electrode is:

PbOa+HS04“+3H++2e=PbS04+2H20

The experiment shows that the discharge capacity of B-Pb02 is always greater than that of a-Pb02. This is because the actual specific surface area of B-Pb02 is larger than Q-Pb02, which directly affects the growth and diffusion of lead sulfate on its surface, thereby affecting the utilization rate of active substances. During the charging and discharging process, n-Pb02 and B-Pb02 are converted to each other, mainly a-Pb02 is converted to 13-Pb02. The charge discharge reaction mechanism of the positive electrode can be divided into dissolution deposition mechanism and solid-state mechanism.

In order to improve the utilization rate of active materials in the positive electrode, various additives are used, including conductive additives, inorganic additives such as bismuth, calcium sulfate, aluminum sulfate, zeolite, as well as organic and polymer additives. Wei Guolin believes through research that various BD additives can greatly improve the capacity of batteries. Significantly improve the utilization rate of active substances, form microstructures with more pores, thereby improving the mass transfer process and significantly enhancing the charging and discharging performance of the positive electrode. The combined effect of BD and PII can significantly improve battery capacity and the utilization rate of positive electrode active material.

Ramanthanll41 research has shown that adding calcium sulfate to the positive electrode active material improves battery performance under high discharge rates and low temperature conditions. Adding RS03H to the positive electrode active material improved the diffusion conditions of H+in the positive electrode micropores, significantly increasing the positive electrode discharge capacity and utilization rate of the positive electrode active material. D. Pavlov and N. CopkOV mixed Pb, 04 and lead powder, and used high-temperature curing to obtain 4PbO · PbS04 paste, which was then used as the positive electrode plate. The cycle life of the battery was increased by 30% due to the presence of a in the active material. The content of Pb02 significantly increases I. Literature 1171 introduces a high-performance positive electrode plate, which adds persulfate to the ordinary lead paste composition. The active material has high porosity and specific surface area, with a discharge power of at least 1W/cm2. The porosity of the active material is 55%, and the specific surface area is at least 4m2/g. Literature [181] proposes adding PbF2 to the lead paste and adding fluororesin latex as a binder without curing, which is conducive to the high-power output of the battery. Some people also propose adding carbon to the active material while using propylene based and propylene based styrene, mainly to facilitate network formation and increase porosity.

1.2.2 Negative electrode active material

The negative electrode active material is lead. When the battery is discharged, the lead negative electrode serves as the anode, and lead oxidizes into Pb, diffusing from the electrode surface into the solution and undergoing a precipitation reaction with 8042-. If the overpotential of the lead electrode is sufficient to cause solid-phase nucleation, a solid-phase reaction can occur, and S042- directly collides with lead to form solid lead sulfate. During the charging process, Pb2+is reduced. Lead can undergo passivation in sulfuric acid solution. To prevent this phenomenon from occurring, sponge lead is used as the negative electrode in production.

In order to improve battery life and capacity, and suppress hydrogen evolution reactions, various expansion agents need to be added to the negative electrode. Negative lead is prone to oxidation during the drying process after formation, and corrosion inhibitors can be added. Common expansion agents include inorganic expansion agents and organic expansion agents. Inorganic expansion agents include barium sulfate, strontium sulfate, carbon black, etc., which are beneficial for electrolyte diffusion, deep discharge, and can delay passivation, as well as prevent electrode specific surface area shrinkage. Organic expansion agents include humic acid, lignin, lignosulfonates, and synthetic tanning agents, which function to prevent electrode specific surface area shrinkage. The commonly used antioxidant inhibitors include α - hydroxy-B-naphthoic acid, glycerol, xylitol, ascorbic acid, rosin, etc., all of which can inhibit lead oxidation.

1.2.3 Battery electrolyte

The electrolyte of the battery is sulfuric acid. Add Na2SO with a concentration of 0.7mol/L to the electrolyte. The capacity of the battery has significantly increased. CoSO。 It is also a type of additive that has been extensively studied by people. Add CoSO to the electrolyte of lead-acid batteries., It can improve the adhesion between the positive electrode active material and the grid, as well as the adhesion between Pb02 particles, effectively increasing the cycle life of the positive electrode grid. (NH4) 2Cr207 electrolyte additive can increase the capacity of lead electrode, accelerate the cathodic and anodic processes of electrode, and improve the overpotential of oxygen evolution. In addition, adding nicotinamide, hydroxylamine compounds, and unsaturated fatty compounds is also beneficial for the lifespan of batteries

1.2.4 Grid

The active material of a battery is usually fixed on a grid made of lead and lead alloy. Lead antimony alloy is an early invented grid alloy, and the antimony content still widely used is 4-6%. Compared with pure lead, lead antimony alloy has good mechanical properties, good castability, low coefficient of thermal expansion, and uniform corrosion. The disadvantages of lead antimony alloy are high resistance, high gas evolution rate, increased battery water loss, and accelerated corrosion of the grid. To achieve this, it is necessary to reduce the antimony content and form low antimony alloys and ultra-low antimony alloys. Low antimony alloys mainly need to solve the hot cracking phenomenon in grid casting, so nucleating agents need to be added, mainly consisting of elements such as s, Se, Cu, and As. The main types of low antimony alloys include silver and bismuth low antimony alloys; Low antimony alloy containing selenium and sulfur; Lead antimony arsenic, lead antimony cadmium, and lead antimony cadmium silver alloys; Lead calcium tin aluminum alloy; Lead strontium tin aluminum alloy, etc.

1.2.5 Partition

The separator is one of the components of a battery, and its main function is to prevent short circuits between the positive and negative electrodes. However, it cannot significantly increase the internal resistance of the battery, and it also allows for the free diffusion of electrolyte and ion migration. In addition, it must have a certain mechanical strength, acid corrosion resistance, and oxidation resistance. The main types of partitions include microporous rubber partitions, sintered polyvinyl chloride microporous plastic partitions, polyvinyl chloride soft plastic partitions, glass fiber and polypropylene partitions, glass fiber partitions, and composite partitions.

Analysis of cycle life of lead-acid batteries

1.2.6 Classification

There are three common classifications for lead-acid batteries.

1) Classified by purpose

China's lead-acid battery products are classified according to their uses. It is mainly divided into several aspects such as starting, fixing, and power. The starting battery is mainly used for starting and lighting various automobiles, locomotives, and ships. Require high current discharge, low-temperature starting, low internal resistance of the battery, and thin positive and negative electrode plates. Fixed lead-acid batteries are mainly used as backup power sources for various large-scale equipment systems, with thick plates, dilute electrolytes, and long service life. Power batteries are mainly used to provide power for various power systems, and both long and short term performance requirements are relatively good.

2) Classified by polar plate structure

It is mainly divided into paste type, tube type, and forming type. Mix lead oxide with sulfuric acid solution to form lead paste, apply it onto a grid made of lead alloy, dry and transform it, and call it a paste coated electrode plate. A skeleton made of lead alloy is covered with woven fiber tubes, which are filled with active substances. This type of electrode plate is called a tubular electrode plate. The electrode plate is made of pure lead

Casting is called forming.

3) Classified by electrolyte and charging maintenance status

Mainly divided into dry discharge batteries, dry charged batteries, wet charged batteries, maintenance free, low maintenance batteries, valve regulated sealed batteries, etc.

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