程新兵， 陈凯， 张典， 沈馨， 吴宇平
东南大学 能源与环境学院， 江苏 南京 211189
引用格式：
程新兵， 陈凯， 张典， 等. 大容量磷酸铁锂电池热安全特征演变规律［J］. 中国粉体技术， 2027， 33（1）： 93-106.
Cheng Xinbing， Chen Kai， Zhang Dian， et al. Evolution mechanisms of thermal safety characteristics in large⁃capacity lithium iron phosphate batteries［J］. China Powder Science and Technology， 2027， 33（1）： 93-106.
DOI：10.13732/j.issn.1008-5548.2027.01.007
收稿日期： 2026-07-03， 修回日期： 2026-07-28， 上线日期： 2026-09-15。
基金项目： 国家自然科学基金项目，编号：92372111。
第一作者： 程新兵（1987—），男，教授，博士，博士生导师，教育部青年长江学者、江苏省杰出青年基金获得者，研究方向为高安全电化学能源工程。E-mail：chengxb@seu.edu.cn。
摘要： 【目的】 为了提升磷酸铁锂电池的安全性能，推动大容量磷酸铁锂电池在电化学储能领域的应用与发展，分析大容量磷酸铁锂电池的热安全特征演变规律。 【研究现状】 综述磷酸铁锂电池和镍钴锰三元锂电池的热失控概率与热失控气体爆燃概率的差异，概括热失控过程中氢气的生成机制以及磷酸铁锂电池热失控气体中氢气比例高的原因，总结电池容量对磷酸铁锂电池热安全特征的影响。 【结论与展望】 提出磷酸铁锂电池的热失控概率较低，但是热失控气体中氢气比例较高，会带来较大爆燃风险；认为电池容量增大导致磷酸铁锂电池的热失控最高温度升高，热失控气体产生量增加，安全性下降；认为针对不同氢气生成机制采取抑制策略以降低热失控气体中氢气比例，同时重视氢气的早期检测和及时预警。
关键词： 氢气； 磷酸铁锂； 锂镍钴锰氧化物； 锂离子电池； 热失控
Abstract
Significance To enhance battery safety， this study comprehensively reviews the evolution mechanisms of thermal safety characteristics in large-capacity lithium iron phosphate batteries， thereby facilitating their development in the field of electrochemical energy storage.
Progress The probabilities of thermal runaway in lithium iron phosphate （LFP） batteries and lithium nickel cobalt manganese oxide （NCM） batteries， as well as the deflagration probabilities of their thermal runaway gases， are comprehensively reviewed. First， the probabilities of thermal runaway in LFP and NCM batteries are compared. This comparison is based on characteristic parameters of thermal runaway， including onset temperature， triggering temperature， maximum temperature， temperature rise rate， accumulated heat， mass loss， and combustion possibility. Next， the hydrogen generation mechanisms during the thermal runaway of lithium-ion batteries are summarized. These mechanisms comprise trace water decomposition， protic species reduction， oligomer decomposition， lithium hydride decomposition， hydrogen fluoride reduction， and binder decomposition. These six hydrogen generation mechanisms are investigated according to their reaction locations and temperatures. All six hydrogen generation mechanisms are localized at the anode. Specifically， the simultaneous participation of both the cathode and anode is required for protic species reduction. Furthermore， five hydrogen generation mechanisms， including trace water decomposition， protic species reduction， oligomer decomposition， lithium hydride decomposition， and hydrogen fluoride reduction， occur simultaneously with the decomposition of the solid electrolyte interphase. Because these five hydrogen generation mechanisms occur at relatively low temperatures， they are classified into the first category. In contrast， binder decomposition takes place at a higher temperature stage. At this point， the solid electrolyte interphase is completely decomposed. Consequently， binder decomposition is assigned to a separate category. The process of hydrogen generation is influenced by the attack of reductive gases on the cathode and oxygen on the anode. As a result， a higher proportion of hydrogen is generated in the thermal runaway gases of LFP batteries than in those of NCM batteries， leading to an increased deflagration probability. Finally， the impact of battery capacity on the thermal safety characteristics of lithium-ion batteries is analyzed. As battery capacity increases， the maximum temperature during thermal runaway increases. Simultaneously， the volume of generated gases increases. These factors pose significant challenges to the application and development of large-capacity lithium-ion batteries.
Conclusions and Prospects Compared to NCM batteries， LFP batteries exhibit higher onset temperature and triggering temperature， and lower maximum temperature， temperature rise rate， accumulated heat， mass loss， and combustion possibility during thermal runaway. This indicates a lower probability of thermal runaway for LFP batteries. However， a higher hydrogen proportion is detected in the thermal runaway gases of LFP batteries， leading to a higher deflagration probability. For traditional small-capacity LFP batteries， the thermal runaway gases exhibit a lower temperature and a smaller volume. The gases are easily cooled and diluted by ambient air. Therefore， deflagration conditions are rarely reached. In contrast， thermal runaway gases with a higher temperature and a larger volume are generated by modern large-capacity LFP batteries. When released into the external environment， the gases deflagrate rapidly. Evidently， the high hydrogen proportion in the thermal runaway gases is the primary cause of the reduced safety of LFP batteries. Therefore， suppression measures based on the six hydrogen generation mechanisms need to be implemented. Regarding trace water decomposition， battery materials must be thoroughly dried. Furthermore， the water content in the assembly environment must be strictly controlled. For protic species reduction， functional separators can be designed as physical barriers. These barriers prevent the diffusion of protic species. Alternatively， the thermal stability of the solid electrolyte interphase can be enhanced by introducing electrolyte additives to prevent the reduction of protic species. Additionally， solid-state electrolytes can serve as physical barriers. However， their electrochemical performance and fabrication processes have certain limitations. To address oligomer decomposition and lithium hydride decomposition， the thermal stability of the solid electrolyte interphase needs to be improved. Regarding hydrogen fluoride reduction， lithium hexafluorophosphate should be replaced with more stable lithium salts. Furthermore， additives capable of scavenging hydrogen fluoride can be introduced into the electrolyte. For binder decomposition， the molecular structure of the binder can be redesigned. For instance， cyclic molecular structures can be used to increase the energy barrier for breaking hydrogen-containing chemical bonds. Alternatively， hydrogen-free binders， such as polytetrafluoroethylene， can be applied. Nevertheless， polytetrafluoroethylene suffers from poor adhesion and low conductivity. Beyond suppressing hydrogen generation， battery safety can also be enhanced through early detection and timely warning. Among the gases released during thermal runaway， hydrogen is the most easily detected. Moreover， its warning time is earlier than that of other gases. Therefore， reliable hydrogen sensors are crucial for the safe operation of battery systems.
Keywords： hydrogen； lithium iron phosphate； lithium nickel cobalt manganese oxide； lithium-ion battery； thermal runaway
参考文献（References）
［1］Shindell D， Smith C J. Climate and air-quality benefits of a realistic phase-out of fossil fuels［J］. Nature， 2019， 573（7774）： 408-411.
［2］Lindley D. Smart grids： the energy storage problem［J］. Nature， 2010， 463（7277）： 18-20.
［3］Chen Kai， Zhang Dian， Jiang Feng， et al. Hydrogen-free cyclized polyacrylonitrile binder enables thermally robust lithium-ion batteries［J］. Particuology， 2026， 115： 25-34.
［4］Fan Ersha， Li Li， Wang Zhenpo， et al. Sustainable recycling technology for Li-ion batteries and beyond： challenges and future prospects［J］. Chemical Reviews， 2020， 120（14）： 7020-7063.
［5］Le P A， Vuong D T， Natsuki J， et al. Overview of the thermal runaway in lithium-ion batteries with application in electric vehicles： working principles， early warning， and future outlooks［J］. Energy & Fuels， 2023， 37（22）： 17052-17074.
［6］García A， Zhao Peng， Monsalve-Serrano J， et al. Optical diagnostics of the venting spray and combustion behaviour during Li-ion battery thermal runaway induced by ramp heating［J］. Applied Thermal Engineering， 2023， 218： 119308.
［7］Jin Yang， Zhao Zhixing， Miao Shan， et al. Explosion hazards study of grid-scale lithium-ion battery energy storage station［J］. Journal of Energy Storage， 2021， 42： 102987.
［8］Song Laifeng， Huang Zonghou， Mei Wenxin， et al. Thermal runaway propagation behavior and energy flow distribution analysis of 280 Ah LiFePO4 battery［J］. Process Safety and Environmental Protection， 2023， 170： 1066-1078.
［9］Conzen J， Lakshmipathy S， Kapahi A， et al. Lithium ion battery energy storage systems （BESS） hazards［J］. Journal of Loss Prevention in the Process Industries， 2023， 81： 104932.
［10］Sarkon G K， Hurdoganoglu D， Eyyamoglu B， et al. Preventing thermal runaway in lithium-ion batteries with nano-porous structures： a critical review［J］. Journal of Power Sources， 2025， 641： 236793.
［11］Shahid S， Agelin-Chaab M. A review of thermal runaway prevention and mitigation strategies for lithium-ion batteries［J］. Energy Conversion and Management： 2022， 16： 100310.
［12］Li Yuxuan， Zhang Ningjie， Jiang Lihua， et al. Assessment of the complete chain evolution process of LIBs from micro interrnal short circuit failure to thermal runaway under mechanical abuse conditions［J］. Process Safety and Environmental Protection， 2024， 185： 296-306.
［13］An Zhoujian， Shi Tianlu， Du Xiaoze， et al. Experimental study on the internal short circuit and failure mechanism of lithium-ion batteries under mechanical abuse conditions［J］. Journal of Energy Storage， 2024， 89： 111819.
［14］Kim H， Sahebzadeh A， Seifert H J， et al. Needle penetration studies on automotive lithium-ion battery cells： influence of resistance between can and positive terminal on thermal runaway［J］. Journal of Power Sources， 2024， 592： 233902.
［15］An Zhoujian， Li Wenda， Du Xiaoze， et al. Experimental study on behaviors of lithium-ion cells experiencing internal short circuit and thermal runaway under nail penetration abuse condition［J］. Applied Thermal Engineering， 2024， 247： 123058.
［16］Xie Xinjing， Wang Zirui， Ouyang Tiancheng. Parametric investigation of thermal runaway mechanism in lithium battery under nail penetration［J］. Energies， 2026， 19（10）： 2274.
［17］Cortada-Torbellino M， Elvira D G， El⁃Aroudi A， et al. Review of lithium-ion battery internal changes due to mechanical loading［J］. Batteries， 2024， 10（7）： 258.
［18］Mao Ning， Zhang Teng， Wang Zhirong， et al. A systematic investigation of internal physical and chemical changes of lithium-ion batteries during overcharge［J］. Journal of Power Sources， 2022， 518： 230767.
［19］Wang Zhenpo， Yuan Jing， Zhu Xiaoqing， et al. Overcharge-to-thermal-runaway behavior and safety assessment of commercial lithium-ion cells with different cathode materials： a comparison study［J］. Journal of Energy Chemistry， 2021， 55： 484-498.
［20］Lei Yu， Xu Lulu， Chan Qing nian， et al. Recent advances in separator design for lithium metal batteries without dendrite formation： implications for electric vehicles［J］. eTransportation， 2024， 20： 100330.
［21］Dai Yixin， Panahi A. Thermal runaway process in lithium-ion batteries： a review［J］. Next Energy， 2025， 6： 100186.
［22］Mallick S， Gayen D. Thermal behaviour and thermal runaway propagation in lithium-ion battery systems-a critical review［J］. Journal of Energy Storage， 2023， 62： 106894.
［23］Huang Zonghou， Li Xin， Wang Qingshan， et al. Experimental investigation on thermal runaway propagation of large format lithium ion battery modules with two cathodes［J］. International Journal of Heat and Mass Transfer， 2021， 172： 121077.
［24］Shen Hengjie， Wang Hewu， Li Minghai， et al. Thermal runaway characteristics and gas composition analysis of lithium-ion batteries with different LFP and NCM cathode materials under inert atmosphere［J］. Electronics， 2023， 12（7）： 1603.
［25］Wei Gang， Huang Ranjun， Zhang Guangxu， et al. A comprehensive insight into the thermal runaway issues in the view of lithium-ion battery intrinsic safety performance and venting gas explosion hazards［J］. Applied Energy， 2023， 349： 121651.
［26］Yang Xinwei， Wang Hewu， Li Minghai， et al. Experimental study on thermal runaway behavior of lithium-ion battery and analysis of combustible limit of gas production［J］. Batteries， 2022， 8（11）： 250.
［27］Yang Mengjie， Rong Mingzhe， Pan Jianbin， et al. Thermal runaway behavior analysis during overheating for commercial LiFePO4 batteries under various state of charges［J］. Applied Thermal Engineering， 2023， 230： 120816.
［28］Bernhard R， Meini S， Gasteiger H A. On-line electrochemical mass spectrometry investigations on the gassing behavior of Li4Ti5O12 electrodes and its origins［J］. Journal of the Electrochemical Society， 2014， 161（4）： A497-A505.
［29］Kim K， Ma H， Park S， et al. Electrolyte-additive-driven interfacial engineering for high-capacity electrodes in lithium-ion batteries： promise and challenges［J］. ACS Energy Letters， 2020， 5（5）： 1537-1553.
［30］Hu Jiangtao， Li Linze， Bi Yujing， et al. Locking oxygen in lattice： a quantifiable comparison of gas generation in polycrystalline and single crystal Ni-rich cathodes［J］. Energy Storage Materials， 2022， 47： 195-202.
［31］Metzger M， Strehle B， Solchenbach S， et al. Origin of H2 evolution in LIBs： H2O reduction vs. electrolyte oxidation［J］. Journal of the Electrochemical Society， 2016， 163（5）： 798-809.
［32］Michan A L， Leskes M， Grey C P. Voltage dependent solid electrolyte interphase formation in silicon electrodes： monitoring the formation of organic decomposition products［J］. Chemistry of Materials， 2016， 28（1）： 385-398.
［33］Owejan J E， Owejan J P， DeCaluwe S C， et al. Solid electrolyte interphase in Li-ion batteries： evolving structures measured in situ by neutron reflectometry［J］. Chemistry of Materials， 2012， 24（11）： 2133-2140.
［34］Liu Xiang， Yin Liang， Ren Dongsheng， et al. In situ observation of thermal-driven degradation and safety concerns of lithiated graphite anode［J］. Nature Communications， 2021， 12： 4235.
［35］Xiang Yuxuan， Tao Mingming， Chen Xiaoxuan， et al. Gas induced formation of inactive Li in rechargeable lithium metal batteries［J］. Nature Communications， 2023， 14： 177.
［36］Liu Mengchuang， Zeng Ziqi， Wu Yuanke， et al. Reviewing recent progress of liquid electrolyte chemistry for mitigating thermal runaway in lithium⁃ion batteries［J］. Energy Storage Materials， 2024， 65： 103133.
［37］Xu Gaojie， Li Jiedong， Wang Chao， et al. The formation/decomposition equilibrium of LiH and its contribution on anode failure in practical lithium metal batteries［J］. Angewandte Chemie International Edition， 2021， 60（14）： 7770-7776.
［38］Logan E R， Hebecker H， Eldesoky A， et al. Performance and degradation of LiFePO4/graphite cells： the impact of water contamination and an evaluation of common electrolyte additives［J］. Journal of the Electrochemical Society， 2020， 167（13）： 130543.
［39］Rinkel B L D， Hall D S， Temprano I， et al. Electrolyte oxidation pathways in lithium-ion batteries［J］. Journal of the American Chemical Society， 2020， 142（35）： 15058-15074.
［40］Peng Yang， Yang Lizhong， Ju Xiaoyu， et al. A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO4 cathode［J］. Journal of Hazardous Materials， 2020， 381： 120916.
［41］Jia Zhuangzhuang， Qin Peng， Li Zheng， et al. Analysis of gas release during the process of thermal runaway of lithium-ion batteries with three different cathode materials［J］. Journal of Energy Storage， 2022， 50： 104302.
［42］Yang Mengjie， Rong Mingzhe， Ye Yijun， et al. Comprehensive analysis of gas production for commercial LiFePO4 batteries during overcharge-thermal runaway［J］. Journal of Energy Storage， 2023， 72： 108323.
［43］Jin Yang， Zheng Zhikun， Wei Donghui， et al. Detection of micro-scale Li dendrite via H2 gas capture for early safety warning［J］. Joule， 2020， 4（8）： 1714-1729.
［44］Song Youzhi， Liu Xiang， Ren Dongsheng， et al. Simultaneously blocking chemical crosstalk and internal short circuit via gel-stretching derived nanoporous non-shrinkage separator for safe lithium-ion batteries［J］. Advanced Materials， 2022， 34（2）： 2106335.
［45］Chen Jingyu， Xu Chengshan， Wang Qinzheng， et al. The thermal-gas coupling mechanism of lithium iron phosphate batteries during thermal runaway［J］. Journal of Power Sources， 2025， 625： 235728.
［46］Feng Xuning， Ouyang Minggao， Liu Xiang， et al. Thermal runaway mechanism of lithium ion battery for electric vehicles： a review［J］. Energy Storage Materials， 2018， 10： 246-267.
［47］Zhang Yuhan， Zhang Shu， Hu Naifang， et al. Oxygen vacancy chemistry in oxide cathodes［J］. Chemical Society Reviews， 2024， 53（7）： 3302-3326.
［48］Liu Xiang， Ren Dongsheng， Hsu H， et al. Thermal runaway of lithium-ion batteries without internal short circuit［J］. Joule， 2018， 2（10）： 2047-2064.
［49］Jia Zhuangzhuang， Wang Shuping， Qin Peng， et al. Comparative investigation of the thermal runaway and gas venting behaviors of large-format LiFePO4 batteries caused by overcharging and overheating［J］. Journal of Energy Storage， 2023， 61： 106791.
［50］Kang Rongxue， Jia Chenxi， Zhao Jinlong， et al. Effects of capacity on the thermal runaway and gas venting behaviors of large-format lithium iron phosphate batteries induced by overcharge［J］. Journal of Energy Storage， 2024， 87： 111523.
［51］Koch S， Fill A， Birke K P. Comprehensive gas analysis on large scale automotive lithium-ion cells in thermal runaway［J］. Journal of Power Sources， 2018， 398： 106-112.
［52］Zheng Tianle， Xu Tonghui， Xiong Jianwei， et al. Multipoint anionic bridge： asymmetric solvation structure improves the stability of lithium-ion batteries［J］. Advanced Science， 2024， 11（48）： 2410329.
［53］Majeed M K， Hussain A， Hussain G， et al. Interfacial engineering of polymer solid-state lithium battery electrolytes and Li-metal anode： current status and future directions［J］. Small， 2024， 20（52）： 2406357.
［54］Chen Xilong， Li Xiangjie， Luo Lingjie， et al. Practical application of all-solid-state lithium batteries based on high-voltage cathodes： challenges and progress［J］. Advanced Energy Materials， 2023， 13（35）： 2301230.
［55］Zhao Jing， Zeng Xiaomin， Wan Zhengwei， et al. M-fluoroiodobenzene electrolyte additive with multifunctional groups for protecting lithium metal anode［J］. Materials Today Energy， 2023， 35： 101328.
［56］Wang Shi， Zhang Lei， Hu Zheng， et al. Intrinsic structural and coordination chemistry insights of Li salts in rechargeable lithium batteries［J］. Advanced Materials， 2025， 37（11）： 2420428.
［57］Huang Tao， Zheng Xiangzhen， Pan Ying， et al. Stabilizing Li-rich layered oxide cathode interface by using silicon-based electrolyte additive［J］. Journal of Colloid and Interface Science， 2024， 662： 527-534.
［58］Chen Kai， Zhang Dian， Guo Jiaxin， et al. Hydrogen generated from binders： an overlooked thermal runaway source in lithium-ion batteries［J］. Journal of Energy Chemistry， 2025， 109： 602-608.
［59］Qin Tian， Yang Haoyi， Li Quan， et al. Design of functional binders for high-specific-energy lithium-ion batteries： from molecular structure to electrode properties［J］. Industrial Chemistry & Materials， 2024， 2（2）： 191-225.
［60］Teng Zhengfu， Lyu Cheng. Detection toward early-stage thermal runaway gases of Li-ion battery by semiconductor sensor［J］. Frontiers in Chemistry， 2025， 13： 1586903.
［61］Li Sixun， Zhou Shiyu， Zhao Shuaiyin， et al. Room temperature resistive hydrogen sensor for early safety warning of Li-ion batteries［J］. Chemosensors， 2023， 11（6）： 344.
［62］Li Long， Zhou Licheng， Chen Yuexi， et al. Precision hydrogen detection in mixed atmospheres using temperature-modula-ted PdAu-In2O3 sensor arrays and machine learning algorithms［J］. Chemical Engineering Journal， 2025， 520： 165633.
［63］Shao Xingyan， Zhang Dongzhi， Tang Mingcong， et al. Amorphous Ag catalytic layer-SnO2 sensitive layer-graphite carbon nitride electron supply layer synergy-enhanced hydrogen gas sensor［J］. Chemical Engineering Journal， 2024， 495： 153676.
