LiNi0.9Co0.05Mn0.05O2 电池的热失控特性和气体分析

Chao Shi, Hewu Wang, Hengjie Shen, Juan Wang, Cheng Li, Yalun Li, Wenqiang Xu, Minghai Li
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The temperature of the battery tabs was measured, revealing that both batteries were in a critical state of thermal runaway near 120 degrees Celsius. A quantitative analysis method was employed during the eruption process, dividing it into three stages: ultra-fast, fast, and slow; the corresponding durations for the two batteries were 3, 2, 27 s and 3, 3, 26 s. By comparing the changes in chamber pressure, it was observed that both batteries exhibited a similar continuous venting duration of 32 s. However, the pressure fluctuation ranges of the two samples were 99.5 and 68.2 kPa·m·s−1. Compared to the other sample, the 211 Ah sample exhibited larger chamber pressure fluctuations and reached higher peak pressures, indicating a higher risk of explosion. In the experimental phenomenon captured by a high-speed camera, it took only 1 s for the sample to transition from the opening of the safety valve to filling the experimental chamber with smoke. The battery with higher energy density exhibited more intense eruption during thermal runaway, resulting in more severe mass loss. The mass loss of the two samples is 73% and 64.87%. The electrolyte also reacted more completely, resulting in a reduced number of measured exhaust components. The main components of gaseous ejections are CO, CO2, H2, C2H4, and CH4. For the 211 Ah battery, the vented gases were mainly composed of CO (41.3%), CO2 (24.8%), H2 (21%), C2H4 (7.4%) and CH4 (3.9%), while those for the other 256 Ah battery were mainly CO (30.6%), CO2 (28.5%), H2 (21.7%), C2H4 (12.4%) and CH4 (5.8%). Comparatively, the higher-capacity battery produced more gases. The gas volumes, converted to standard conditions (0 °C, 101 kPa) and normalized, resulted in 1.985 L/Ah and 2.182 L/Ah, respectively. The results provide valuable guidance for the protection of large-capacity, high-energy-density battery systems. 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摘要

高镍含量的三元层状材料具有高容量、低成本和相对较好的安全性等优点,被认为是最有前途的高能量密度锂离子电池正极材料。然而,随着三元层状材料中镍含量的增加,其热稳定性明显下降。因此,探索锂离子电池的热失控特性至关重要。本研究将两块高镍锂离子电池(LiNi0.9Co0.05Mn0.05O2)在充满氮气的密封室内横向加热至热失控,以研究其热特性和气体成分。对电池片的温度进行了测量,结果表明两种电池都处于接近 120 摄氏度的热失控临界状态。在喷发过程中采用了定量分析方法,将其分为超快、快和慢三个阶段;两个电池的相应持续时间分别为 3、2、27 秒和 3、3、26 秒。与另一个样品相比,211 Ah 样品的腔室压力波动更大,峰值压力更高,表明爆炸风险更高。在高速摄像机捕捉到的实验现象中,样品从打开安全阀到烟雾充满实验箱只用了 1 秒钟。能量密度较高的电池在热失控过程中表现出更强烈的爆发,导致更严重的质量损失。两个样品的质量损失分别为 73% 和 64.87%。电解液的反应也更完全,导致测量到的废气成分数量减少。气体喷出物的主要成分是 CO、CO2、H2、C2H4 和 CH4。容量为 211 Ah 的电池排出的气体主要包括 CO(41.3%)、CO2(24.8%)、H2(21%)、C2H4(7.4%)和 CH4(3.9%),而容量为 256 Ah 的电池排出的气体主要包括 CO(30.6%)、CO2(28.5%)、H2(21.7%)、C2H4(12.4%)和 CH4(5.8%)。相比之下,容量更大的电池产生的气体更多。将气体体积转换为标准条件(0 °C、101 kPa)并归一化后,结果分别为 1.985 L/Ah 和 2.182 L/Ah。这些结果为保护大容量、高能量密度电池系统提供了宝贵的指导。对爆发过程的定量分析为火灾报警系统和消防策略提供了帮助。
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Thermal Runaway Characteristics and Gas Analysis of LiNi0.9Co0.05Mn0.05O2 Batteries
Layered ternary materials with high nickel content are regarded as the most promising cathode materials for high-energy-density lithium-ion batteries, owing to their advantages of high capacity, low cost, and relatively good safety. However, as the nickel content increases in ternary layered materials, their thermal stability noticeably decreases. It is of paramount importance to explore the characteristics of thermal runaway for lithium-ion batteries. In this study, two high-nickel LiNi0.9Co0.05Mn0.05O2 batteries were laterally heated to thermal runaway in a sealed chamber filled with nitrogen to investigate the thermal characteristics and gas compositions. The temperature of the battery tabs was measured, revealing that both batteries were in a critical state of thermal runaway near 120 degrees Celsius. A quantitative analysis method was employed during the eruption process, dividing it into three stages: ultra-fast, fast, and slow; the corresponding durations for the two batteries were 3, 2, 27 s and 3, 3, 26 s. By comparing the changes in chamber pressure, it was observed that both batteries exhibited a similar continuous venting duration of 32 s. However, the pressure fluctuation ranges of the two samples were 99.5 and 68.2 kPa·m·s−1. Compared to the other sample, the 211 Ah sample exhibited larger chamber pressure fluctuations and reached higher peak pressures, indicating a higher risk of explosion. In the experimental phenomenon captured by a high-speed camera, it took only 1 s for the sample to transition from the opening of the safety valve to filling the experimental chamber with smoke. The battery with higher energy density exhibited more intense eruption during thermal runaway, resulting in more severe mass loss. The mass loss of the two samples is 73% and 64.87%. The electrolyte also reacted more completely, resulting in a reduced number of measured exhaust components. The main components of gaseous ejections are CO, CO2, H2, C2H4, and CH4. For the 211 Ah battery, the vented gases were mainly composed of CO (41.3%), CO2 (24.8%), H2 (21%), C2H4 (7.4%) and CH4 (3.9%), while those for the other 256 Ah battery were mainly CO (30.6%), CO2 (28.5%), H2 (21.7%), C2H4 (12.4%) and CH4 (5.8%). Comparatively, the higher-capacity battery produced more gases. The gas volumes, converted to standard conditions (0 °C, 101 kPa) and normalized, resulted in 1.985 L/Ah and 2.182 L/Ah, respectively. The results provide valuable guidance for the protection of large-capacity, high-energy-density battery systems. The quantitative analysis of the eruption process has provided assistance to fire alarm systems and firefighting strategies.
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