锂离子电池电解液热失控是诱发电池火灾事故的主要原因，其热失控反应主要包括热解、释能及燃烧三个阶段。电解液热失控过程会产生大量可燃、有毒的气体产物并伴随剧烈的热量释放，严重威胁了储能系统安全。为明确电解液热失控反应机理，获取电解液热失控反应特征参数，并量化阻燃添加剂对电解液热失控反应的抑制效能，本文采用理论分析、数值模拟计算和实验室实验结合的方法，分析电解液热解产热、产气对其热失控行为的诱发作用，探究电解液热失控释能对其燃烧行为的加速作用，明确电解液热失控燃烧的火灾风险，最终结合宏微观方法得到甲基磷酸二甲酯（DMMP）对电解液热失控抑制路径和抑制效能。主要研究内容及成果如下：

（1）开展锂离子电池电解液热解行为实验，对比分析溶剂种类、溶剂比例及升温速率对电解液热解反应特性的影响规律，获取电解液热解反应特征参数；构建电解液热解反应分子动力学模型，明确电解液热解产物种类及其分布比例，阐明电解液热解产气规律及生成路径，发现CO、CO₂和H₂是电解液热解反应主要的气体产物，总占比的77.12%~98.82%，链状碳酸酯比例增加，电解液可燃性指数增大2.51~3.84倍，热稳定性显著降低，热解反应更为剧烈。

（2）通过锂离子电池电解液释能行为实验，分析溶剂种类及热通量对电解液释能排气行为及燃烧行为的影响规律，获取电解液释能行为特征参数。研究发现当热通量超过10.00 kW/m²时，电解液将面临极高的火灾风险，且触发三元电解液释能行为所需的热通量比二元电解液更低；依据电解液释能特征参数划分电解液释能行为特征阶段，界定电解液不同释能阶段释温升速率及气体射流种类，确定电解液释能过程最高温度达394.81 ℃，排气行为触发温度为184.78 ℃~259.55 ℃。

（3）依据多因素影响下锂离子电池电解液燃烧特性实验结果，量化分析热通量及溶剂组成对电解液燃烧特性参数的影响规律，解析电解液燃烧阶段式演化过程，得到电解液组分与其燃烧特征参数间的内在关系；阐明电解液燃烧动力学行为与其热-质传递机制的内在关联，分析电解液直径及溶剂种类对电解液火焰行为的影响规律，构建对流模式下电解液燃烧行为多因素关联模型。结合电解液热解反应特性、释能行为特征及燃烧动力学行为，最终揭示锂离子电池电解液热失控反应机理。

（4）采用化学反应动力学方法，得到甲基磷酸二甲酯（DMMP）对电解液活性自由基、气体产物及层流燃烧速度的抑制路径，发现DMMP消耗氢自由基的倾向性高于羟基自由基，PO₂+H+M=HOPO+M是DMMP抑制电解液热失控的主要路径；通过自熄时间、释能行为及燃烧行为实验发现，添加10%的DMMP可使电解液由可燃性转为耐燃性，有效延缓了电解液释能行为触发时间，并显著降低了电解液燃烧风险，且相同添加量下DMMP对DMC的抑制效能更显著；综合评估DMMP对电解液电化学性能和安全性能的影响，最终确定10%的DMMP是阻燃电解液选择的最优添加量。

通过以上研究，从反应路径上完善了锂离子电池电解液热失控演化机理的理论模型，得出了电解液燃烧行为多因素关联模型，揭示了DMMP对电解液热失控反应的抑制路径，并通过多参数量化了DMMP对电解液热失控行为的抑制效能。研究结果丰富了锂离子电池电解液热失控理论体系，为高安全性电解液体系的优化设计与技术创新提供了理论支撑，具有重要的应用价值。

Thermal runaway of lithium-ion battery electrolytes is a primary cause of battery fire incidents, involving three key stages: pyrolysis, energy release, and combustion. This process generates large quantities of flammable and toxic gases accompanied by intense heat release, posing severe threats to energy storage system safety. To elucidate the reaction mechanism of electrolyte thermal runaway, obtain characteristic parameters, and quantify the inhibitory efficacy of flame retardant additives, this study integrates theoretical analysis, numerical simulation, and laboratory experiments. The work investigates the roles of electrolyte pyrolysis heat/gas generation in triggering thermal runaway, explores the acceleration effect of energy release on combustion behavior, evaluates the fire hazards of electrolyte combustion, and ultimately identifies the inhibition pathways and efficacy of dimethyl methyl phosphonate (DMMP) through macro- and micro-scale approaches. The main research content and findings are as follows:

(1) Pyrolysis behavior experiments were conducted to analyze the effects of solvent type, solvent ratio, and heating rate on electrolyte pyrolysis characteristics, obtaining key reaction parameters. A molecular dynamics model of electrolyte pyrolysis reaction was constructed to make clear the types of electrolyte pyrolysis products and their distribution ratios, and to elucidate the law of electrolyte pyrolysis gas production and its path of generation, and it was found that CO, CO₂ and H₂ were the main gas products of electrolyte pyrolysis reaction, accounting for 77.12%~98.82% of the total proportion. Increasing linear carbonate content elevated the flammability index by 2.51~3.84 times, significantly reducing thermal stability and intensifying pyrolysis reactions.

(2) Energy release experiments examined the influence of solvent type and heat flux on exhaust and combustion behavior, determining characteristic parameters. At heat fluxes exceeding 10.00 kW/m², electrolytes face extreme fire risks, with ternary electrolytes requiring lower heat fluxes for energy release than binary systems. Energy release stages were classified based on temperature rise rates and gas jet types, with peak temperatures reaching 394.81 °C and exhaust initiation occurring at 184.78 ℃–259.55°C.

(3) Combustion experiments quantified the effects of heat flux and solvent composition on combustion parameters, deciphered the staged evolution process, and established correlations between electrolyte components and combustion characteristics. The intrinsic link between combustion kinetics and heat/mass transfer mechanisms was elucidated, with flame behavior analyzed under varying diameters and solvent types. A multi-factor coupling model for convective-mode combustion was developed, culminating in a comprehensive mechanism for electrolyte thermal runaway.

(4) Chemical kinetics analysis identified DMMP’s inhibition pathways via scavenging active radicals (preferentially H· over OH·), altering gas products, and reducing laminar flame speed, with PO₂+H+M=HOPO+M as the dominant pathway. Self-extinguishing time, energy release, and combustion tests demonstrated that 10% DMMP transformed electrolytes from flammable to flame-retardant, delayed energy release ignition, and markedly mitigated combustion risks, with superior efficacy for DMC. Electrochemical and safety evaluations confirmed 10% DMMP as the optimal additive.

This study advances the theoretical framework of lithium-ion battery electrolyte thermal runaway by refining its reaction pathways, establishing a multifactor-coupled combustion model, and elucidating the inhibition mechanisms of DMMP. Through multiparameter analysis, the inhibitory efficacy of DMMP on thermal runaway behavior was quantitatively evaluated. The findings enrich the fundamental understanding of electrolyte thermal runaway and provide critical theoretical support for the optimized design and technological innovation of high-safety electrolyte systems, demonstrating significant practical applications.

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