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磷酸鐵鋰在鋰離子電池中的研究進展

Research progress of lithium iron phosphate in lithium-ion batteries

  • 摘要: 作為21世紀鋰離子動力電池潛在的“綠色”正極材料,橄欖石型磷酸鐵鋰(LiFePO4,LFP)因其理論比容量(170 mA·h·g?1)高、電壓平臺(3.5 V (vs Li/Li+))穩定、安全性高、原料價格低廉且來源豐富、環境友好等優點而受到越來越廣泛的關注. 然而,較低的電子電導率和鋰離子擴散速率影響了LFP的電化學性能和低溫性能. 此外,LFP振實密度較低,導致體積能量密度較低,一定程度上也限制了其進一步應用. 目前,LFP正朝著高能量密度、長循環壽命方向發展. 研究人員通過不斷探索LFP的充放電原理來優化合成路線,并嘗試碳包覆、摻雜改性、納米化等方法來提高材料的性能. 基于上述研究,分析總結了LFP的結構、制備方法及其優缺點、改性策略及回收利用等,并對LFP的發展趨勢進行了展望.

     

    Abstract: Currently, the Earth’s limited resources, the escalating oil crisis, rapid industrial development, and considerable population growth have increased the demand for sustainable energy production and storage systems. A crucial factor in addressing these problems is the development of optimal electrode materials with desirable electrochemical properties. Lithium-ion batteries (LIBs) are the most promising and fastest growing electrical energy storage system. Over the past decade, LIBs have seen substantial growth in industries such as electric vehicles and industrial power generation systems due to their high operating voltage, high specific energy, fast charging and discharging capabilities, wide operating temperature range, long service life, and high environmental safety. LIBs primarily comprise cathode materials, anode materials, electrolytes, and diaphragms. Since their commercialization, cathode materials have been a key research focus due to their influence on energy and power density as well as cost. Recent investigations have been exploring lithium battery electrode materials with abundant resources, low cost, and high energy density. Olivine-type lithium iron phosphate (LiFePO4, LFP) is emerging as a potential “green” cathode material for LIBs in the 21st century, focusing on high energy density, long cycle life, low cost, and environmentally friendly. Compared to traditional polyanionic cathode materials, LFP has gained increasing attention due to its high theoretical specific capacity (170 mA·h·g?1), stable voltage platform (3.5 V (vs Li/Li+)), excellent safety performance, and the abundance and low cost of its raw materials. At present, lithium iron phosphate is primarily used in the new energy automotive industry and the energy storage market. Owing to these advantages, LFP has received widespread attention as a promising cathode material for LIBs. However, its lower electronic conductivity and lithium-ion diffusion rate, along with its reduced vibrational density, hinder the electrochemical and low-temperature performance of LFP. These factors lead to lower volumetric energy densities, limiting their further applications to some extent. Consequently, these issues considerably inhibit the development of LFP. At present, improving the conductivity and lithium-ion diffusion rate of LFP has become a key focus of researchers. After years of efforts, researchers have optimized the synthesis process by exploring the charging and discharging principles of LFP. They have also explored various new techniques, processes, equipment, and materials, as well as employing methods such as carbon coating, doping modifications, and nanosizing to enhance LFP performance. This paper outlines the preparation of LFP using six methods: high-temperature solid-phase method, carbothermal reduction method, sol–gel method, hydrothermal synthesis method, coprecipitation, and microwave methods. The paper also discusses the advantages and disadvantages of each preparation method. Various modification strategies for LFP, including carbon capping, ion doping, nanosizing and the use of quantum dots, are also comprehensively reviewed. Additionally, five recycling methods are described: hydrometallurgy, pyrometallurgy, high-temperature solid-phase remediation, bioleaching, and direct regeneration. Finally, the paper offers an outlook on the future development trends of LFP.

     

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