Review of Thermal Runaway Evolution Mechanism and Active Protection Strategy for Lithium-Ion Energy Storage Systems Based on Catastrophe Theory

doi:10.16628/j.cnki.2095-8188.2026.04.007

Abstract

Abstract:

Lithium-ion energy storage systems are the core key to the construction of new power systems, while safety risks including thermal runaway and electrical faults seriously restrict their large-scale application. Aiming at building a comprehensive energy storage safety technical system, three key fields, including risk evolution mechanism, multi-dimensional monitoring and diagnosis, and high-efficiency protection strategy, are systematically reviewed. The technical progress from material modification to intelligent algorithm is summarized, and the existing challenges of current technologies in complex working condition adaptability and cost control are deeply analyzed.In the future, the full life-cycle management based on multi-field coupling simulation and artificial intelligence intelligent early warning will become the mainstream development direction. The research indicates that constructing a closed-loop intelligent system of“risk prediction, accurate monitoring and efficient protection”is an inevitable way to realize the safe and sustainable development of energy storage industry.

Key words: lithium-ion energy storage system, energy storage safety, thermal runaway, safety early warning, intelligent operation and maintenance

CLC Number:

TM911

ZHANG Hongquan, LIU Mingyuan, CHEN Xinghao, SUN Biao, XIE Yuxuan. Review of Thermal Runaway Evolution Mechanism and Active Protection Strategy for Lithium-Ion Energy Storage Systems Based on Catastrophe Theory[J]. LOW VOLTAGE APPARATUS, 2026, 0(4): 57-68.

Figures/Tables 12

References 51

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反应阶段	起始温度范围/℃	主要产热反应	热力学特性(产热量)	关键作用与影响
SEI膜分解	90~120	SEI膜中有机组分分解	弱放热	链式反应触发点,破坏负极保护层,暴露高活性反应界面
负极与电解液反应	120~250	嵌锂石墨与电解液还原反应	强放热	主要放热阶段之一,产热率大,是温升的关键驱动力
隔膜熔融/内短路	130~150	隔膜熔化,正负极接触导致内短路	产热量巨大, 取决于SOC	动力学转折点,由化学产热转为电-热耦合产热,导致温度跃升
正极分解	180~250 (依赖于材料)	正极材料晶格分解并释放氧气	强放热	反应放大器,释氧行为是导致起火爆炸的关键因素。三元材料比磷酸铁锂剧烈
电解质燃烧/爆炸	>250	电解液与正极释放的氧气燃烧	极强放热	最终失效形式,反应速率极快,导致电池破裂和火焰喷射

反应发生区域	诱发与类型条件	反应机理与主要产物
负极:SEI膜热分解与重构	高温(C>90 ℃),充放电体积呼吸	亚稳态有机组分分解产物:Li₂CO₃,C₂H₄,CO₂
负极:析锂	低温充电、大倍率过充、负极过量比低	Li⁺ +e^-→Li⁰ 产物:锂枝晶、死锂
正极:晶格结构相变	高电压(>4.5 V),深度脱锂、高温	层状→尖晶石→岩盐相产物:晶格畸变、析氧
正极:电解液氧化(CEI生长)	高电压、高SOC状态	溶剂在高电位下氧化脱氢产物:厚CEI膜,CO₂,CO
交互作用:过渡金属溶解	电解液酸化(HF腐蚀),正极材料老化	Mn²⁺/Ni²⁺溶出并迁移产物:负极表面沉积金属
电解质:锂盐分解与水解	微量水分、高温	LiPF₆→LiF+PF₅ PF₅+H₂O→HF+POF₃
集流体:腐蚀与溶解	过放电(Cu)、高电压(Al)	Cu→Cu²⁺(氧化),Al钝化膜破坏(点蚀)

监测技术维度	关键信号指标	响应时效性 (相对于TR触发)	信号灵敏度	工程部署难度	成本	综述评价与适用场景
基础电热监测	电压、电流、表面温度	滞后(TR中后期)	低(受采样精度限制)	低(BMS标配)	低	基础防线。不可或缺,但对局部热点和微短路存在“盲区”,不能作为唯一预警源
内阻监测	AC/DC 阻抗	中等(老化演变期)	中	高(需在线激励)	中	SOH诊断辅助。适用于长周期健康度评估,但在突发性机械滥用下响应较慢
气体监测	CO,H₂	提前(5~15 min)	极高 (ppm级)	中(需优化气路)	中高	关键增量技术。能有效识别不可逆副反应的起始点,是目前提升系统安全冗余性价比最优的方案
机械/ 声学监测	膨胀力、声发射	实时/提前	高	极高 (需结构改造)	极高	前沿探索。具备内部状态透视能力,目前多见于高端实验场景或特种应用