How many times does the lead-acid battery cycle?

In order to prevent corrosion of the positive grid, a multi-component low tantalum alloy was developed. The corrosion resistance of this multi-alloy is greatly improved. The negative grid is made of lead-plated copper. The ratio of the weight of the copper grid to the active material is 1:3, and the specific energy of the reservoir is significantly improved. Moreover, due to the good electrical performance of the copper grid negative electrode, the charging acceptance capability is strong, and the battery charge and discharge cycle life is raised. Adding additives to the positive and negative active materials increases the utilization rate of the active materials and prolongs the service life. In order to prevent the lead-free short circuit, a comprehensive short-circuit prevention measures are taken. High performance boards and a range of new assembly processes are used.

Introduction to the development of lead-acid batteries

Lead-acid battery was first made by Gaston prandtl in 1860. It has a history of more than 140 years. Over the past one hundred years, with the development of science and technology, lead-acid battery technology, structure, production mechanization and automation degree of continuous improvement, performance continuously improved. Because of its excellent performance and price ratio, until today the production and application of lead-acid battery is still in the first place of various chemical power supply. Its application mainly includes power, starting, emergency and working power supply, the object of use includes vehicles, ships, aircraft, telecommunications systems, computers, instruments and other equipment, facilities, especially in automotive batteries and industrial batteries, lead-acid batteries occupy more than 90% of the market share, with an absolute advantage of 121. The original Valta reactor first appeared in 1800. In 1801, gottelot had observed what is called a "secondary current", which is the current that can be obtained after charging in the opposite direction from the charging current. From 1836 to 1843, Della zouvi studied Pb02 as a positive electrode in sulfuric acid solution. Several types of electrodes for lead-acid batteries and the main manufacturing processes were developed in the first half century between 1860 and 1910. The first was the formation plate. In 1881 foer put forward the first paste plate. Xie lang was the first to use Pb. Sb alloy gate is designed to improve the fluidity of liquid alloys and the hardness of solid alloys. In 1924, R shimazu himself invented the ball mill, and used ball mill powder instead of red lead powder as the active material of the battery. Lignin was used as a negative active material additive to prevent lead sulfate from crystallizing and prolong the life of the battery. In the 1920s there were microporous rubber partitions, and in the 1940s there were resin and paper partitions, which gradually replaced wooden partitions. During the 20 years from the 1950s to the 1960s, lead-acid batteries made significant progress in the manufacturing process in several aspects. Thin plate and improved grid design; The technology of through wall welding applied to starting battery; Generally adopt low antimony or antimony free alloy casting grid; Improve the utilization rate of active material in short time discharge; Dry - charge battery manufacturing process. After the 1970s, countries have vigorously developed maintenance-free and sealed lead-acid battery roar in the basic theory, physics, especially the achievements and means of electronics are widely used: stable potentiometer, scanning current meter, scanning electron microscope, x. X-ray and neutron diffraction,special magnetic resonance and electron spectroscopy plus rotating disc electrodes and computer technology. The focus of the research has shifted from thermodynamics to electrode process dynamics.

The main producers of lead-acid batteries are distributed in several developed countries including the United States, Europe (UK, Germany, France, etc.) and Japan, and their total output accounts for about 70% of the world's total output. The United States has EXIDE Technologies, the world's largest producer of lead-acid batteries (with annual global sales of $2.8 billion), and other very large lead-acid battery manufacturers such as JOHNSON, CONTROL, DEKA, and DELPHI. The output value of lead-acid batteries in the United States accounts for about 20% of the world's total. However, in recent years, with the changes in factors such as technology and labor costs, some lead-acid battery companies have experienced a decline. The production of lead-acid batteries is transferred to countries such as India, Southeast Asia and other countries where labor costs are low. There are many large lead acid battery manufacturers in Europe, such as CHLORIDE, HOPPECKE, F1AMM, DETA, HAWKER, etc. Lead-acid batteries in Europe play an important role in the world, with a well-established technology-leading lead-acid battery manufacturer such as Sunshine (now a subsidiary of EXIDE). In 2001, the output of lead-acid batteries in Europe was 48.1 million, and in 2002 it was estimated to be 49.1 million. In 2005, it will reach 51.8 million. In terms of industrial batteries, the number of spare batteries in 2000 was 130,000, the number of sealed batteries less than 24 Ah was 110,000, and the number of sealed batteries larger than 24 Ah was 430,000. The producers of lead-acid batteries in Japan mainly include Yuasa Battery Co., Ltd. , Matsushita Battery Co., Ltd., Furukawa Battery Co., Ltd., Shin-Kobe Electric Co., Ltd., and Japan Battery (GS). According to statistics from relevant parties, in 2002, the output value of lead-acid batteries in Japan was about 1.16 billion US dollars, the starting batteries of lead-acid batteries accounted for 55.7%, and the industrial batteries (fixed lead-acid batteries) accounted for 6.7%. Small lead acid battery accounts for 8. O%, the other 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 been greatly improved, and the energy of weight ratio and volume ratio has been greatly improved. Less maintenance and maintenance-free, valve-regulated sealed lead-acid batteries are growing rapidly.

Lead-acid battery structure, composition and classification

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

The main structure of the lead-acid battery includes a positive electrode, a negative electrode, a separator, a sulfuric acid electrolyte, a battery tank, and a cover. The positive and negative electrodes are respectively welded into a pole group, and the large-capacity battery is led out from the bus bar to form a pole. The electrolyte used in the lead-acid battery is a certain concentration of sulfuric acid electrolyte. The function of the rain separator 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 resistant, and has sufficient porosity and pore size to allow electrolyte and the ions pass freely. The tank body is also an electrical insulator, which is resistant to acid and temperature, and has high mechanical strength. Generally, hard rubber or plastic is used as the tank body.

Lead acid battery cycle life analysis

1.2.1 Positive active material

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

The Pb02 electrode reaction is:

PbOa+HS04"+3H++2e=PbS04+2H20

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

In order to improve the utilization rate of the active material of the positive electrode, various additives, including conductive additives, inorganic additives such as barium, calcium sulfate, aluminum sulfate, zeolite, and the like, and organic and polymer additives are used. Wei Guolin believes that the BD additive can greatly improve the battery capacity. Significantly improve the utilization rate of active materials, can form a microstructure with more pores, thereby improving the mass transfer process and significantly improving the charge and discharge performance of the positive electrode. The combination of BD and PII can significantly increase the battery capacity and the utilization rate of the positive active material.

Ramanthanll41 studies have shown that calcium sulphate is added to the positive active material to improve battery performance at high discharge rates and low temperatures. The addition of RS03H to the positive electrode active material improves the diffusion condition of H+ in the positive electrode micropores, and greatly increases the positive electrode discharge capacity and the positive electrode active material utilization rate 115]. D. Pavlov and N. CopkOV mixes Pb, 04 and lead powder, and obtains 4PbO·PbS04 paste as a positive electrode after high temperature curing. The cycle life of the battery is increased by 30% because of the active substance a. The content of Pb02 is significantly increased by I". Document 1171 introduces a high-performance positive electrode plate with persulfate added to the common lead paste composition, the active material has high porosity and specific surface area, and the discharge power is at least 1 W/cm2. The material has a porosity of 55% and a specific surface area of at least 4 ㎡/g. The literature [181 proposes to add PbF2 to the lead paste and add fluororesin latex as a binder, which does not require curing, which is beneficial to the high power output of the battery. It is proposed to use propylene and propylene styrene while adding carbon to the active material, which is mainly beneficial to the formation of a network and increases the porosity.

1.2.2 Negative active material

The negative electrode active material is lead. When the battery is discharged, the lead anode is an anode, and the lead is oxidized to Pb", which diffuses from the surface of the electrode into the solution, and a precipitation reaction occurs with the 8042. If the lead electrode is over potential enough to cause solid phase nucleation, a solid phase reaction may occur. S042 directly collides with lead to form solid lead sulfate, and Pb2+ is reduced during charging. Lead can be passivated in sulfuric acid solution. In order to prevent this from happening, sponge lead is used as a negative electrode in production.

In order to improve battery life and capacity and suppress hydrogen evolution reaction, it is necessary to add various expansion agents to the negative electrode. The negative electrode lead is easily oxidized in the drying step after the formation, and a corrosion inhibitor can be added. Commonly used expansion agents are inorganic expansion agents and organic expansion agents. Inorganic expansion agents include barium sulfate, barium sulfate, carbon black, etc., which facilitate the diffusion of the electrolyte, facilitate deep discharge, delay the passivation, and prevent the specific surface area of the electrode from shrinking. The organic swelling agent includes humic acid, lignin, lignosulfonate, and synthetic tanning agent, and functions to prevent the specific surface area of the electrode from shrinking. Common anti-oxidation inhibitors are a-hydroxy B-naminic acid, glycerin, xylitol, ascorbic acid, rosin, etc., all of which can inhibit lead oxidation.

1.2.3 Battery electrolyte

The battery electrolyte is sulfuric acid. Add a concentration of 0 to the electrolyte. At 7mol/L of Na2SO, the battery capacity was significantly improved. CoSO is also a kind of additive that people study more. The addition of CoSO in the electrolyte of lead battery can improve the adhesion between the positive active material and the grid, as well as the adhesion between Pb02 particles, thus effectively improving the cycle life of the positive grid. (NH4) 2Cr207 electrolyte additive can increase the capacity of lead electrode, accelerate the process of cathode and anode of electrode, and improve the overpotential of oxygen precipitation. In addition, the addition of niacinamide, hydroxylamine group compounds, and unsaturated aliphatic compounds on the battery life is also beneficial

1.2.4 Grid

The battery active material is usually fixed to a grid made of lead and lead alloy. Lead-bismuth alloys are the grid alloys invented earlier, and the germanium content still widely used is 4 to 6%. Compared with pure lead, lead-bismuth alloy has good mechanical properties, good castability, low thermal expansion coefficient and uniform corrosion. The disadvantages of lead-bismuth alloys are large electrical resistance, high gassing rate, increased water loss of the battery, and accelerated corrosion of the grid. To this end, it is necessary to reduce the niobium content to form a low niobium alloy and an ultra low niobium alloy. Low-ruthenium alloys mainly need to solve the thermal cracking phenomenon in grid casting. Therefore, it is necessary to add a nucleating agent. The nucleating agents are mainly s, Se, cu and As. The main low-lying alloys are silver-containing and antimony-barium alloys; selenium- and sulfur-containing low-bismuth alloys; lead-bismuth-arsenide, lead-cadmium-cadmium and lead-cadmium-silver alloys; lead-calcium-tin-aluminum alloys;

1.2.5 Partition

The separator is one of the components of the battery, its main role is to prevent short circuit between positive and negative. However, it does not significantly increase the internal resistance of the battery, but also allows the electrolyte to diffuse freely and ionize. In addition, it must have certain mechanical strength, acid corrosion resistance and oxidation resistance. The main types of separators are microporous rubber separators, sintered polyvinyl chloride microporous plastic separators, polyvinyl chloride flexible plastic separators, glass fiber and polypropylene separators, glass filament separators and composite separators.

Lead acid battery cycle life analysis

1.2.6 Classification

Lead-acid batteries are customarily used in three classifications.

1) Classified by purpose

China's lead-acid battery products are classified by use. It is mainly divided into several aspects such as starting use, fixed use and power use. The starting battery is mainly used for starting and lighting of various automobiles, locomotives and ships. It is required to discharge at a high current, can start at a low temperature, the internal resistance of the battery should be small, and the positive and negative plates should be thin. The fixed lead-acid battery is mainly used as a backup power source for various large-scale equipment systems, the plate is thick, the electrolyte is thin, and the service life is long. The power battery mainly provides power for various power systems, and the long-term and short-time performance requirements are better.

2) Classification by plate structure

It is mainly divided into paste type, tube type and forming type. The lead oxide is adjusted into a lead paste with a sulfuric acid solution, coated on a grid cast with a lead alloy, and dried and formed into a paste-like plate. The skeleton is made of a lead alloy, and the fibrous tube is prepared in the skeleton outer casing, and the tube is filled with an active material. This electrode plate is called a tubular plate. Plate by pure lead

Casting is called forming.

3) Classified by electrolyte and charge maintenance

Mainly divided into dry discharge battery, dry charged battery, wet charged battery, maintenance free, less maintenance battery, valve control sealed battery.

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