LR03 alkaline battery

Development of production technology of positive electrode materials for rechargeable LR03 alkaline battery

This paper reviews the development history of production and preparation technology of positive electrode materials for lithium-ion batteries and analyzes the development direction of positive electrode materials for lithium-ion batteries. At the end of the last century, from the perspective of processing performance and battery performance of positive electrode materials for lithium-ion batteries, the research team of Tsinghua University proposed a technology for preparing high-density spherical precursors by controlling crystallization, and combined with the subsequent solid-phase sintering process, proposed an industrial technology for preparing lithium-containing electrode materials.

Among them, the controlled crystallization method for preparing precursors can regulate and optimize the performance of materials at four levels: unit cell structure, primary particle composition and morphology, secondary particle size and morphology, and particle surface chemistry. The materials produced by this technology process have the characteristics of easy control of particle size and morphology, good uniformity, batch consistency and stability, and can simultaneously meet the comprehensive requirements of batteries for material electrochemical properties and processing properties. Due to the high packing density of the material, it is particularly suitable for high specific energy batteries.

This technology process is applicable to a variety of positive electrode materials and is suitable for large-scale production. As time goes by, it has gradually been proven to be the best production technology process for positive electrode materials for lithium-ion batteries, and has been widely accepted and recognized by the current industry. This is also one of the important contributions made by Chinese scientists to the international lithium-ion battery industry.

Lithium-ion batteries have the advantages of high specific energy, high energy storage efficiency and long life. In recent years, they have gradually occupied an important market share in electric vehicles, energy storage systems and mobile electronic devices. Since Sony Corporation of Japan took the lead in commercializing lithium-ion batteries in 1990, the negative electrode material has always been carbon-based material, while the positive electrode material has made great progress and is the most critical material to promote the performance of lithium-ion batteries.

The research and development of positive electrode materials for lithium-ion batteries are mainly carried out in three aspects: 1) At the basic science level, it is important to discover new materials, or to calculate, design and synthesize the composition, crystal structure and defect structure of materials, in order to discover new positive electrode materials with excellent electrochemical performance; 2) At the material chemistry level, it is important to explore the synthesis technology, in order to optimize the material structure factors such as the crystal structure, orientation, particle morphology, interface, etc. of the material, and obtain the best match between the electrochemical performance, processing performance and battery performance, with the purpose of developing the material structure and its synthesis method that can achieve the best comprehensive performance of positive electrode materials; 3) At the material engineering technology level, it is important to develop large-scale, low-cost and stable equipment and processes, in order to develop reasonable engineering technology to meet market demand.

In order for the positive electrode materials of lithium-ion batteries to play the best performance in the whole battery, it is necessary to further optimize the physical and chemical properties of the materials such as crystal structure, particle structure and morphology, particle surface chemistry, material stacking density and compaction density, etc. on the premise of optimizing the material composition, and at the same time, strictly prevent the introduction of trace metal impurities in the process. Of course, stable and high-quality large-scale production is an important guarantee for the stable performance of materials in battery manufacturing. As lithium battery technology improves and the lithium battery market matures, the application fields of different cathode materials are gradually divided, that is, the performance requirements of lithium-ion batteries for various cathode materials are also different. Therefore, the mainstream synthesis technology and process of cathode materials have also experienced different development paths.

1. Performance requirements of lithium-ion batteries for cathode materials

(1) Industry performance requirements for lithium-ion batteries

To understand the technical indicators of cathode materials, we must first talk about the technical indicators of batteries. In the early days of the lithium-ion battery industry, it mainly served the development of mobile electronic products, such as laptops, tablets, mobile smart terminals (mobile phones), etc. In recent years, the new energy industry and the electric vehicle industry have risen rapidly, and the demand for lithium-ion batteries has risen rapidly, stimulating the lithium battery industry to accelerate its development. Therefore, lithium-ion batteries must meet many technical performance indicators in order to be recognized by the industry and further developed.

Among these technical indicators, the most basic ones are specific energy, cycle stability, specific power, cost, safety and reliability, durability, manufacturing efficiency, sustainability, etc. The indicators are interrelated, and different application fields have different priorities for lithium-ion battery indicators. Compared with lithium-ion batteries in portable electronic products, the biggest difference between lithium-ion batteries used in energy storage and electric vehicle industries is that the capacity of single cells has increased by ten times or even dozens of times, and the complexity of the functions, structures and applications of battery modules has increased significantly, which has put forward higher requirements for the consistency and reliability of lithium-ion batteries.

Based on more than 20 years of research and engineering practice experience, it is believed that the most important technical indicators of lithium-ion batteries are specific energy and cycle performance, followed by specific power, safety, reliability, cost and consistency. The higher the specific energy, the lower the material cost per unit energy (Wh); the longer the cycle life, the lower the actual cost of the battery. At present, lithium-ion batteries for mobile smart terminals must meet the requirements of specific energy of more than 700Wh/L and cycle performance of more than 200 times, while lithium-ion batteries for electric vehicles must meet the requirements of specific energy of more than 140Wh/kg (lithium iron phosphate or lithium manganese oxide positive electrode materials) or 200Wh/kg (layered oxide positive electrode materials) and cycle performance of more than 1,500 times. Lithium-ion battery positive electrode materials must meet the above battery indicators before they can be accepted by the mainstream battery market. At present, the specific energy and cycle performance of lithium-ion batteries depend mainly on the cathode material [1-6]. Therefore, the important research and development goals of lithium-ion battery cathode materials are high specific energy and long cycle life.

For lithium-ion batteries used in laptops, tablets, and mobile smart terminals, volume specific energy is the most important indicator. Of course, batteries with high volume specific energy usually have high mass specific energy. Because customers want to put more battery energy in a device of a certain volume (such as a mobile phone), the graphite/lithium cobalt oxide system lithium-ion batteries are the most mature in industrialization and have the highest volume specific energy. Lithium-ion batteries of other material systems are unlikely to shake the dominant position of lithium-ion batteries of this system in the mobile electronic product industry. Safety, reliability, and certain cycle performance are also important for this type of battery. Since it is mainly used in a monomer mode, the consistency and cost of the battery are not so important.

For lithium-ion batteries used in electric vehicles, although their requirements for volume specific energy are not as stringent as those for portable electronic product batteries, after all, the space of passenger cars is limited, and the weight of the car body will affect the mileage of electric vehicles. Therefore, the mass specific energy and volume specific energy of the battery are still very important. In addition, automotive lithium-ion batteries have almost stringent requirements for all other performances, far exceeding the performance requirements of portable electronic product batteries. There are three biggest differences between automotive lithium-ion batteries and portable electronic product batteries.

First, electric vehicle power sources require higher voltages and currents, and require a large number of single cells to be connected in series and parallel. This means that the specific energy that can actually be used by the battery pack depends not only on the specific energy of the single cell, but also on the consistency of the single cell, especially the dynamic consistency. The consistency of power LR03 alkaline battery has gradually attracted people's attention in recent years [7]. Second, the scale of single cells has increased significantly, which makes the price of single cells higher, and the harm caused by thermal runaway is more serious. Therefore, the market is more sensitive to the safety and reliability of batteries. Third, since electric vehicles have a service life of 10-15 years, the requirements for cycle performance are very high, generally more than 1,500 times. In addition, since electric vehicles need to start and accelerate, there are certain requirements for the comparative power of power LR03 alkaline battery.

With the rapid development of the electric vehicle industry, power lithium-ion batteries will become the mainstream products of the lithium battery industry together with portable electronic product batteries in the future. Specific energy and cycle performance are the most important performance indicators that are always

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