Research on Thermal Runaway Mechanism and Reaction Kinetics Analysis for NCM622 Ternary Battery
Xu Chengrong1,2, Sun Bingxiang1,2, Zhou Xingzhen1,2, Zhu Xiyan1,2, Zhang Weige1,2
1. National Active Distribution Network Technology Research Center (NANTEC) Beijing Jiaotong University Beijing 100044 China; 2. Key Lab of Vehicular Multi-Energy Drive Systems (VMEDS) Ministry of Education Beijing Jiaotong University Beijing 100044 China
Abstract：With the widespread adoption of high-nickel ternary lithium-ion batteries in electric vehicles and unmanned aerial vehicles, the thermal runaway risks associated with high energy density have become increasingly prominent. Current research on the thermal stability of high-nickel ternary cathode materials predominantly focuses on systems with NCM811 or higher nickel content, whereas thermal runaway mechanisms in NCM622 batteries remain underexplored. In particular, there is a significant lack of complete kinetic parameters for material side reactions throughout the thermal runaway process. This paper examines a commercial 50 A·h NCM622/graphite ternary pouch cell, providing theoretical support for battery safety design and thermal-runaway early-warning systems. The experimental procedure involved adiabatic thermal-runaway tests with EV-ARC operating in the “Heat-Wait-Seek” (HWS) mode. It enabled the acquisition of key thermal parameters, including the self-heating onset temperature (T1≈75℃), thermal runaway trigger temperature (T2≈180℃), and maximum temperature (T3>1 000℃). Simultaneously, the thermal flow of various battery components and their combinations was analyzed using differential scanning calorimetry (DSC). The results identified the “anode-electrolyte reaction” and the “cathode-anode reaction” as the two primary heat sources during thermal runaway, with specific heat generation values of 1 201.11 J·g-1 and 3 061.25 J·g-1, respectively. By integrating the observed separator shrinkage temperature (approximately 150℃) with the multi-stage exothermic behavior, the battery thermal runaway process was categorized into five distinct characteristic stages. Then, an autocatalytic concentration function, $f_{x}\left(c_{x}\right)=c_{x}^{m_{x}}\left(1-c_{x}\right)^{n_{x}}$, was introduced to construct the reaction kinetic equations. This function describes the self-accelerating reaction behavior of battery materials during thermal runaway. For the nine key exothermic reactions (Q1~Q9) identified in the “anode+electrolyte” and “cathode+anode” sample groups, a hybrid parameter identification method was employed. The Kissinger method was combined with the particle swarm optimization (PSO) algorithm to determine the kinetic parameters for each reaction, including activation energy (Ea), pre-exponential factor (Ax), reaction orders (mx, nx), and reaction enthalpy (ΔHx). Simulation results with different heating rates (5, 10, 15, and 20℃/min) agree with experimental DSC data. The root-mean-square errors (RMSEs) for the two sample groups were 0.107 5 and 0.300 1, respectively. This approach achieved quantitative decoupling of the heat generation from all exothermic reactions. This research analyzed the thermal runaway mechanism in NCM622 batteries and decoupled thermal contributions, providing critical data for early warning of thermal runaway and safety management of NCM622 batteries. Future work will focus on integrating these results with intelligent diagnostic algorithms that fuse multiple parameters, thereby advancing battery management systems (BMS).
[1] 黄辰悦, 郑鸿飞, 秦宁, 等. 单晶高镍三元正极材料: 挑战与策略[J]. 物理化学学报, 2024, 40(9): 35-55. Huang Chenyue, Zheng Hongfei, Qin Ning, et al.Single-crystal nickel-rich cathode materials: challenges and strategies[J]. Acta Physico-Chimica Sinica, 2024, 40(9): 35-55. [2] 邓七九, 田聪聪, 凤帅帅, 等. 锂离子电池高镍三元正极材料LiNi1-x-yCoxMnyO2的改性研究进展[J]. 电源学报, 2019, 17(5): 153-161. Deng Qijiu, Tian Congcong, Feng Shuaishuai, et al.Research progress in modifications of Ni-rich ternary cathode material (LiNi1-x-yCoxMnyO2) for lithium-ion batteries[J]. Journal of Power Supply, 2019, 17(5): 153-161. [3] E Jiaqiang, Xiao Hanxu, Tian Sicheng, et al. A comprehensive review on thermal runaway model of a lithium-ion battery: Mechanism, thermal, mechanical, propagation, gas venting and combustion[J]. Rene- wable Energy, 2024, 229: 120762. [4] Feng Xuning, Ren Dongsheng, He Xiangming, et al.Mitigating thermal runaway of lithium-ion batteries[J]. Joule, 2020, 4(4): 743-770. [5] 张跃强, 田君, 赵鼎, 等. 高镍三元电池热反应机理及其改善性研究进展[J]. 电源技术, 2019, 43(7): 1223-1225, 1229. Zhang Yueqiang, Tian Jun, Zhao Ding, et al.Research progress of thermal reaction mechanism and thermal stability improvement for Ni-rich lithium-ion batteries[J]. Chinese Journal of Power Sources, 2019, 43(7): 1223-1225, 1229. [6] 王天宇, 王丽, 孙伟, 等. 高镍三元材料的研究进展[J]. 化学进展, 2024, 36(7): 1026-1045. Wang Tianyu, Wang Li, Sun Wei, et al.Research progress of Ni-rich cathode materials[J]. Progress in Chemistry, 2024, 36(7): 1026-1045. [7] 马敬轩, 赖铱麟, 吕娜伟, 等. 锂离子电池智能传感监测及预警技术[J]. 电工技术学报, 2025, 40(3): 941-963. Ma Jingxuan, Lai Yilin, Lü Nawei, et al.Lithium-ion battery intelligent sensing monitoring and early warning technology[J]. Transactions of China Elec- trotechnical Society, 2025, 40(3): 941-963. [8] 冯旭宁. 车用锂离子动力电池热失控诱发与扩展机理、建模与防控[D]. 北京: 清华大学, 2016. Feng Xuning.Thermal runaway initiation and propagation of lithium-ion traction battery for electric vehicle: test, modeling and prevention[D]. Beijing: Tsinghua University, 2016. [9] Zhang Guangxu, Wei Xuezhe, Tang Xuan, et al.Internal short circuit mechanisms, experimental approaches and detection methods of lithium-ion batteries for electric vehicles: a review[J]. Renewable and Sustainable Energy Reviews, 2021, 141: 110790. [10] Dai Yixin, Panahi A.Thermal runaway process in lithium-ion batteries: a review[J]. Next Energy, 2025, 6: 100186. [11] 马敬轩, 赖铱麟, 吕娜伟, 等. 锂离子电池智能传感监测及预警技术[J]. 电工技术学报, 2025, 40(3): 941-963. Ma Jingxuan, Lai Yilin, Lü Nawei, et al.Lithium-ion battery intelligent sensing monitoring and early warning technology[J]. Transactions of China Elec- trotechnical Society, 2025, 40(3): 941-963. [12] 李坤, 黄锐, 丛君, 等. NCM622正极材料结构形态和储锂特性的同步演变[J]. 化工学报, 2025, 76(4): 1831-1840. Li Kun, Huang Rui, Cong Jun, et al.Simultaneous evolution of structural morphology and lithium storage properties in NCM622 cathode material[J]. CIESC Journal, 2025, 76(4): 1831-1840. [13] 祁万虎, 王大辉, 陈怀敬, 等. 硫酸氢钾焙烧法回收NCM622正极材料中金属的研究[J]. 中国材料进展, 2024, 43(5): 374-379. Qi Wanhu, Wang Dahui, Chen Huaijing, et al.Study on extraction of metal from NCM622 cathode material by potassium bisulfate roasting[J]. Materials China, 2024, 43(5): 374-379. [14] 李明起. 锂离子电池正极材料LiNi0.6Co0.2Mn0.2O2的改性研究[D]. 上海: 上海大学, 2023. Li Mingqi.Modification of LiNi0.6Co0.2Mn0.2O2 cathode materials for lithium ion batteries[D]. Shanghai: Shanghai University, 2023. [15] 杜光超, 郑莉莉, 张志超, 等. 圆柱形高镍三元锂离子电池高温热失控实验研究[J]. 储能科学与技术, 2020, 9(1): 249-256. Du Guangchao, Zheng Lili, Zhang Zhichao, et al.Experimental study on high temperature thermal runaway of cylindrical high nickel ternary lithium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(1): 249-256. [16] 王莉, 冯旭宁, 薛钢, 等. 锂离子电池安全性评估的ARC测试方法和数据分析[J]. 储能科学与技术, 2018, 7(6): 1261-1270. Wang Li, Feng Xuning, Xue Gang, et al.ARC experimental and data analysis for safety evaluation of Li-ion batteries[J]. Energy Storage Science and Technology, 2018, 7(6): 1261-1270. [17] Zheng Siqi, Wang Li, Feng Xuning, et al.Probing the heat sources during thermal runaway process by thermal analysis of different battery chemistries[J]. Journal of Power Sources, 2018, 378: 527-536. [18] 袁奥特, 蔡涛, 刘政辰, 等. 基于电化学阻抗谱的锂离子电池电滥用失效预警研究[J]. 电工技术学报, 2025, 40(7): 2306-2321. Yuan Aote, Cai Tao, Liu Zhengchen, et al.Study of electrical abuse failure early warning of lithium-ion batteries based on electrochemical impedance spec- troscopy[J]. Transactions of China Electrotechnical Society, 2025, 40(7): 2306-2321. [19] 张平林, 秦超, 张超俊, 等. 基于极限梯度提升算法的梯次电池热失控预警技术研究[J]. 电气技术, 2026, 27(4): 18-23, 32. Zhang Pinglin, Qin Chao, Zhang Chaojun, et al.Research on thermal runaway warning technology for cascaded batteries based on extreme gradient boosting algorithm[J]. Electrical Engineering, 2026, 27(4): 18-23, 32. [20] Zhao Liqi, Hou Junxian, Feng Xuning, et al.The trade-off characteristic between battery thermal runaway and combustion[J]. Energy Storage Materials, 2024, 69: 103380. [21] 陈杰. 高比能量锂离子电池热滥用失效机理与建模研究[D]. 北京: 北京交通大学, 2022. Chen Jie.Mechanism and modeling of thermal abuse failure of high specific energy lithium-ion battery[D]. Beijing: Beijing Jiaotong University, 2022. [22] 贾隆舟, 郑莉莉, 王栋, 等. 高镍三元正极材料锂离子电池的热失控分析[J]. 电池, 2022, 52(1): 58-62. Jia Longzhou, Zheng Lili, Wang Dong, et al.Analysis of high nickel ternary cathode materials on thermal runaway of Li-ion battery[J]. Battery Bimonthly, 2022, 52(1): 58-62. [23] Li Hao, Wu X, Fang Sheng, et al.Study on the electrical-thermal properties of lithium-ion battery materials in the NCM622/graphite system[J]. Frontiers in Chemistry, 2024, 12: 1403696. [24] Ren Dongsheng, Feng Xuning, Lu Languang, et al.Overcharge behaviors and failure mechanism of lithium-ion batteries under different test conditions[J]. Applied Energy, 2019, 250: 323-332. [25] Zhang Yue, Cheng Siyuan, Mei Wenxin, et al.Understanding of thermal runaway mechanism of LiFePO4 battery in-depth by three-level analysis[J]. Applied Energy, 2023, 336: 120695. [26] Wang Yu, Ren Dongsheng, Feng Xuning, et al.Thermal runaway modeling of large format high- nickel/silicon-graphite lithium-ion batteries based on reaction sequence and kinetics[J]. Applied Energy, 2022, 306: 117943. [27] Nie Baisheng, Dong Yunshuo, Chang Li.The evolution of thermal runaway parameters of lithium-ion batteries under different abuse conditions: a review[J]. Journal of Energy Storage, 2024, 96: 112624.
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