A comparative study on the degradation behaviors of overcharged lithium-ion batteries under different ambient temperatures

In the current work, a series of experiments are carried out to investigate the degradation behavior of lithium-ion batteries during overcharge cycling, as well as the influence of ambient temperature on the degradation. In which, different charge cut-off voltages (4.5, 4.8, and 5.0 V) and ambient temperatures (0°C, 20°C, 50°C, and 70 °C) are included. During the overcharge process, the batteries demonstrate severe temperature rises, and several key electrochemical parameters such as the charge capacity, energy density, median voltage, and resistances all increase, revealing the deterioration of heat generation and electrode kinetics. Besides that, batteries exhibit serious degradation behavior during the overcharge cycling, which is presented through the evolution of battery temperature curves, charge voltage curves, and internal resistance curves. Moreover, the severity of degradation exacerbates with the increasing overcharge degree. Finally, it is found that deep-overcharged batteries may be more sensitive to the ambient temperature than slight-overcharged ones, where an abusive temperature can significantly aggravate the corresponding degradation.     

软包和硬壳磷酸铁锂单体电池过充热传播研究

为了研究硬壳和软包磷酸铁锂单体电池过充工况下对周围电池的热辐射影响,本文研究了磷酸铁锂软包和硬壳电池在仅单体、两单体电池紧贴和两单体电池相距1cm三种工况下的热传播行为。试验以0.5C恒定电流分别对48Ah的软包和24Ah的硬壳电池进行过充,利用可见光监控、红外监控、多路温度记录仪分别对电池外部形貌、外部温度和电池表面温度变化进行实时监测。研究表明,过充阶段,硬壳过充电池温升65.5℃,平均温升速率0.0392℃/s;软包过充电池温升57.3℃,平均温升速率0.0143℃/s;相邻硬壳电池最高温升44℃,最大温升速率0.0312℃/s;相邻软包电池最高温升7.9℃,最高温升速率0.0063℃/s;软包电池过充后,产生的膨胀力对相邻电池影响更大,相邻电池产生的机械应力较大。试验结果可为研究模组内部硬壳或软包磷酸铁锂电池之间的热辐射影响提供理论和实验参考。     

Experimental investigation on the essential cause of the degrading performances for an overcharging ternary battery

Ternary power batteries, as the mainstream power sources of electric vehicles, are liable to inducing thermal runaway (TR) with respect to their sensitivity to abusive conditions. Among various abuse conditions, the overcharge of a battery has been considered as the most common and severe case giving rise to thermal safety accidents. In this study, an overcharged battery and a normal battery, both using ternary/graphite electrodes, were investigated and analyzed synergistically through thermal behaviors and electrochemical characteristics. Initially, a series of electrochemical parameters including charge and discharge voltage plateaus, discharged capacity and time at different discharge rates, and internal resistances were carried out. Then, the heat generation behaviors between normal and overcharged batteries were evaluated. Furtherly, the interconnectedness with the electrochemical capacity degradation and heat generation aggravation of the ternary battery after overcharge was analyzed. Besides, the essential causes of the deterioration of electrochemical properties and severe heat behaviors resulting from overcharge were intensively analyzed via microscopic perspectives. In addition, the electrochemical characteristics fading of abused ternary battery triggered by overcharge were investigated, especially under higher temperature (55°C) and ultralow temperature (−20°C) conditions. Therefore, for an overcharged battery, this research not only elaborates the essential causa of the degraded electrochemical and anabatic thermal performance from a materials and thermal science perspective but also provides a foundation for further promoting the safety properties of commercialized power batteries with ternary chemical systems.     

软包动力电池过充电热失控特征研究

研究了正极和负极分别为8系高镍三元NCM811（Li（Ni0.8Mn0.1O0.1）O2）和硅碳（SiOx/graphite）的25 Ah软包动力电池过充电触发热失控特征。结合电池材料热特性和热失控产气成分分析,揭示了绝热与非绝热环境下,电池热失控期间内部微观变化和动态产热特性。过充电触发热失控的路径为：过充电超过安全边界电压后电池内部发生副反应和内部极片微短路,引起气体和热量累积,最终电池过热达到热失控临界点。与非绝热环境相比,绝热环境下热失控触发瞬间温度高出37.5 ℃,且触发时长有不同程度的缩短（约为90～500 s）。最后对电池的安全和失效边界做出了界定。     

锂离子电池过充电行为研究

从充电倍率、负极材料的种类以及正负极材料的电容量匹配等方面,研究了锂离子电池的过充电行为.结果表明:当以低倍率(0.1C和0.5C)过充电时,电池仍可维持密封完好状态;当电池以高倍率(如1C)过充电时,电池的气阀被冲开,内部电芯的温度高达182℃,比电池壳表面的温度高出80℃.在相同电容量匹配的情况下,负极材料的种类对电池过充电的影响很小;正极过量越多,电池的电压平台越长,电压曲线也越不平滑,电池壳表面达到的最高温度也越高;正极量的变化比负极量的变化对锂离子电池过充电行为的影响更大.     

过充电对 MCMB-LiCoO2电池性能的影响

组装了以中间相炭微球（MCMB）为负极、LiCoO2为正极、金属锂为参比电极的从型三电极锂离子蓄电池,通过对三电极电池在过充电时、过充电前后的性能测试,及正负极对锂参比电极的电位测试,并结合XRD和SEM实验,研究了过充电对MCMB-LiCoO2锂离子蓄电池的性能影响。结果表明：当电池过充电至4,8V时,电池表现出较高的充放电容量,但容量衰减较快,循环稳定性较差,且电池在放电初期时的放电曲线呈凸弧形。过充电导致的正极材料LiCoO2相结构的变化、正负电极表面钝化膜的增长变厚,以及正极集流体铝箔的氧化腐蚀,是电池性能迅速恶化的主要原因。     

添加剂、隔膜对锂离子电池过充性能的影响

采用电聚合添加剂环己基苯、联苯来改善以钴酸锂为正极材料的高容量锂离子方形电池过充性能(1 C 10 V、3 C4.8 V),并探讨隔膜性能对电池过充测试的影响。实验发现,1 C 10 V过充测试,电解液中添加环己基量增加时能提高电池过充测试的通过率,添加5%(质量分数)环己基苯+5%(质量分数)联苯时能对电池起到良好的保护效果,但对3 C 4.8V所起的作用不大;具有较大的穿刺强度的隔膜能对电池3 C 4.8 V过充测试起到良好的保护作用;隔膜型号与添加剂对电池循环厚度及容量保持率均有一定的影响,加入添加剂后电池循环性能下降,而良好的隔膜性能可提高电池循环性能。     

不同倍率下磷酸铁锂电池模组过充热失控特性研究

随着电化学储能技术在电力系统中的广泛应用,电化学储能技术的安全性越来越受到重视。文中以储能用磷酸铁锂电池模组(8.8 kW·h, 25.6 V,344 A·h)为研究对象,进行3次不同倍率(0.4C,0.5C,1C)的恒流过充试验,研究其在不同充电倍率条件下的过充热失控特性,并辅以starccm+软件进行热场仿真计算。结果表明,电池模组在额定充电倍率0.5C(172 A)和1C(344 A)下持续过充会发生起火,起火时间随着充电倍率增加而减少;充电倍率对磷酸铁锂电池模组过充行为特性影响较大,随着充电倍率的增加,热失控最高温度和峰值电压升高,过充测试时间随着充电倍率的升高而降低;不同充电倍率条件下,电池安全阀首次打开时的电压均为1.7倍额定电压,可以进一步研究以作为电池热失控预警参数。文中研究成果可为规模化储能用磷酸铁锂电池的安全性研究和电池管理系统(BMS)对过充故障的安全管理提供参考。     

锂离子电池过充保护添加剂shuttle的研究

通过在锂离子电池电解液中添加2,5-二叔丁基-1,4-二甲氧基苯(2,5-diterbutyl-1,4-dimethoxybenzene,简称shuttle)来提高电池的过充保护能力。对磷酸铁锂电池分别进行了循环伏安扫描、常温循环寿命、过充后循环、交流阻抗测试,实验结果表明,在1 mol/L LiPF6/(EC+DEC+EMC)(1∶1∶1)+1%VC电解液中添加2%(质量分数)shuttle,当电压为3.81 V(相对于Li/Li+)时,shuttle开始发生氧化反应,烷氧基发生氧化离解,消耗电池内部过充的电量,提高了锂离子电池的安全性。此外,添加2%(质量分数)shuttle后电池循环性能有所提高,循环180次后,容量保持率从91.60%提高至94.70%。     

锂离子电池过充保护添加剂的进展

论述了电聚合添加剂,如联苯、环己苯、二甲苯、3-氯甲氧基苯和4-溴苯基异氰酸酯等以及氧化还原对添加剂,如2,5-二特丁基-1,4-二甲氧基苯、4-特丁基-1,2-二甲氧基苯、2,5-二氟-1,4-二甲氧基苯和2-五氟基苯-四氟-1,3,2-苯基二氧硼等锂离子电池过充保护添加剂的研究进展.对过充保护添加剂的前景进行了预测.