摘要
[背景]锂离子电池凭借其低成本和高能量密度,在当今清洁和高效能源领域发挥着越来越重要的作用.然而,电动汽车和储能电站的电池日历老化现象会显著影响其使用寿命.因此,深入了解锂离子电池的日历老化机制,对改进电池管理系统和优化电池制造工艺,提升电池综合性能至关重要.[进展]本文总结了近年来锂离子电池日历老化的研究进展,归纳和探讨了环境温度、存储时间、荷电状态和动态存储条件对锂离子电池日历老化的影响.此外,从负极固体电解质界面的生长、存储过程电解液的分解和正极过渡金属的溶出等方面总结了锂离子电池日历老化机制和相关表征技术,分析了不同老化机制对电池性能的影响,并总结了日历老化模型的研究进展.[展望]目前日历老化的研究仍存在实际工况下电池老化行为不明确、缺乏老化过程定量表征等问题,通过设计合理的日历老化路径,结合先进的表征技术,有望深入理解锂离子电池的日历老化机制,为锂离子电池的设计和寿命预测提供理论依据和参考.
[Background]In recent years,with the rapid development of energy storage systems,lithium-ion batteries have become crucial for the energy storage applications due to their low cost and high energy density.However,prolonged periods of inactivity in electric vehicles and energy storage power stations lead to calendar aging in these batteries.During storage,complex chemical and electrochemical processes cause self-discharge inside the batteries,resulting in capacity degradation and increased resistance,which significantly affect battery lifetime.Therefore,a comprehensive understanding of the aging mechanisms in lithium-ion batteries is essential for enhancing battery management systems and optimizing manufacturing processes to improve overall performance of batteries.[Progress]This paper provides an overview of recent research progress on the factors influencing calendar aging and aging mechanisms of lithium-ion batteries,emphasizing the effects of ambient temperature,storage time,state of charge(SOC),and dynamic storage.Calendar aging accelerates with increased temperature,storage time,and SOC,resulting in varied aging behaviors under different conditions.The relationship between capacity fade and time is non-linear during storage,with the battery capacity decaying faster initially and then slowing over time.The aging behaviors differ significantly between high and low temperature storage.High temperature storage markedly accelerates the aging rate of the battery,while low temperature storage slows the parasitic reactions rate and reduces the self-discharge rate.The effect of storage SOC on battery capacity aging can be categorized into three regions,including low,medium,and high SOC ranges.Batteries stored at high SOC experience greater capacity degradation,whereas those stored at low SOC show minimal degradation.During dynamic storage aging,battery aging conditions constantly vary throughout the testing procedure,providing data that more accurately depict battery aging behaviors under real operation conditions.The different sequences of temperatures and SOCs have a minor effect on aging behavior,whereas varying sequences of storage and cyclic aging affect the overall aging of the battery.In addition,the mechanisms of calendar aging and related characterization techniques of lithium-ion batteries are analyzed in terms of the solid electrolyte interphase(SEI)on the anode,electrolyte decomposition,and the dissolution of transition metals in the cathode.As the storage time increases,the SEI thickens,with high temperature storage leading to the transformation of the organic component into a denser inorganic component of the SEI.Furthermore,electrolyte decomposition accelerates at elevated temperatures and high SOC,and the interface reactions between the electrolyte and electrodes are aggravated,enhancing the reaction activity of electrolyte decomposition.The dissolution of transition metals in the cathode is significantly influenced by calendar aging conditions as well,which increases with higher temperatures,SOC,and longer storage time.Moreover,the various structures of cathode active materials also have impact on transition metals dissolution.Finally,research progress on calendar aging model is summarized.Empirical data-based models suggest a square root relationship between calendar aging capacity degradation and time,consistent with SEI growth observed during calendar aging.[Perspective]Current research on calendar aging still faces challenges,such as unclear aging behaviors of batteries under practical operation conditions and the lack of quantitative characterization of the aging process.Integrating a reasonable-designed calendar aging path with advanced characterization techniques is expected to provide a comprehensive understanding of the calendar aging mechanisms in lithium-ion batteries.Such efforts can serve as a foundational basic and reference for improving battery design and lifespan prediction.
作者
龚正良
温芳梅
汤士军
胡泳钢
GONG Zhengliang;WEN Fangmei;TANG Shijun;HU Yonggang(College of Energy,Xiamen University,Xiamen 361102,China;College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)
出处
《厦门大学学报(自然科学版)》
北大核心
2025年第1期31-44,共14页
Journal of Xiamen University:Natural Science
基金
国家重点研发计划(2021YFB2401800)。
关键词
锂离子电池
日历老化
老化因素
老化机制
lithium-ion battery
calendar aging
aging factor
aging mechanism
