在锂离子电池(LIB)热失控(TR)的能量流分析中,对流换热系数(h根据雷诺数(Re),射流过程被划分为三个阶段——层流、过渡流与湍流Re基于此分类方法,努塞尔数(Nusselt number)Nu)通过半经验对流换热关联式确定了整个喷射过程中的对流换热系数。进一步结合混合燃料费的物性参数,最终量化了对流换热系数的动态变化,由此建立了电池热失控期间能量传递的动态分析方法。此外,本研究系统探究了荷电状态(SOC)对此过程的影响机制。研究结果表明,以荷电状态(SOC)为75%的电池为例,热失控(TR)过程中会出现两种截然不同的喷射行为,分别对应163.7°C和332.3°C的峰值电池温度。爆炸指数(Kst这两股射流的( )分别为2.83 kPa·m·s和15.36 kPa·m·s,其可燃范围在4.91%至35.84%之间。第二股射流第VI阶段期间,−1−1Nu以及h分别达到389.90和1350.78 W·m-2。%%在能量分布方面,对流传热对总能量传递的贡献率显著提升,从阶段IV的1.24%增至阶段VI的8.47%。最终,本研究通过整合包括%%)作为核心参数。然而存在关键研究空白:现有研究缺乏对锂离子电池热失控过程中瞬态对流传热系数的动态表征,且喷射行为与能量传递的关联机制仍不明确——这构成本研究解决的核心科学问题。主要研究目标是通过建立热失控期间能量传递的动态分析方法,填补这一空白,并揭示荷电状态(SOC)对喷射特性与能量流耦合关系的影响。为实现这一目标,本研究开发了锂离子电池热失控(TR)实验平台。实验在密闭环境中进行,期间同步监测商用锂离子动力电池(以下简称“电池”)正极、负极、安全阀表面温度以及实验舱内部温度与压力。采用气相色谱仪对热失控过程中产生的气体组分进行定量分析,并基于理想气体状态方程计算了逸出气体的流速。, respectively. Regarding energy distribution, the contribution of convective heat transfer to total energy transfer increased significantly, from 1.24 % in Stage IV to 8.47 % in Stage VI. Finally, this study established a TR risk evaluation system for batteries at different SOC levels (25 %, 50 %, 75 %, 100 %) by integrating key parameters, including −2−1Re,Nu,h,KLIB,以及峰值温度。风险等级排序为:100% SOC >75% SOC >50% SOC >25% SOC。本研究实现了对电池热失控过程中能量传递过程的动态分析,并提出了一种将喷射参数与能量流相关联的方法,从而为电池安全设计、定量风险评估及预防性控制策略的制定提供了重要理论与实验基础。
锂离子电池凭借其高能量密度和长循环寿命的核心优势,已在电动汽车、储能系统等领域获得广泛应用[[1], [2], [3], [4], [5], [6]]。相关数据预测[7]显示,到2030年全球LIB出货量有望达到5.1太瓦时。尽管学术界和工业界针对电池管理[8,9]、电池材料优化[10,11]以及健康状态(SOH)[12]等领域开展了大量研究,旨在保障电池运行稳定性并实现风险早期预警,但车载锂离子电池热失控事件仍时有发生。一旦被Trigger,锂离子电池热失控风险极易引发燃烧、爆炸等严重安全事故,并伴随剧烈放热反应和有毒气体释放。此类危害不仅对人员安全和生态环境构成重大威胁,更成为制约锂离子电池技术进一步发展与规模化应用的关键瓶颈[[13], [14], [15], [16], [17]]。现有实验研究主要通过热滥用、电滥用和机械滥用[18]等方式探究锂离子电池的热失控现象。此外,多项研究还考察了荷电状态(SOC)、充电速率及大气压力等附加因素对热失控触发与蔓延过程[[19], [20], [21]]的影响。 锂电池中的TR(热失控)本质上是一种由热量与燃料费之间正反馈循环驱动的级联链式反应。Yang等人[2]对NCM622、NCM811、NCM9/0.5/0.5和LFP电池的热失控产气特性进行了对比研究,发现所有案例中的主要气体成分均包含CO、CO2、C2、H4、CH %%2, 和 C4尽管各自比例存在差异。Zhang等[22]研究了不同荷电状态(SOC)对2.2Ah 18650型二氧化钴正极锂电池热失控过程中燃料费释放的影响。100% SOC电池在热失控时表现出最复杂的气体组分,包含从C2Hx到C8Hx的烃类及醇类等31种化合物;而0% SOC电池仅释放四种气体:CO、CO22, 和 C2和C2H42与低荷电状态(SOC)电池相比,100% SOC电池的热失控气体中不饱和烃占比显著更高。如表1所示,该过程始于低温阶段(80–120°C)下固体电解质界面膜(SEI膜)的热分解反应。该反应不仅产生烷烃类气体,更重要的是破坏了负极表面的钝化层,为后续剧烈放热反应创造了条件。6随后在90–250°C温度区间内,裸露的锂化负极与电解质发生剧烈还原反应,生成大量可燃气体如氢气(H)、乙烯(C2)和一氧化碳(CO),同时释放大量热量。这成为系统温升的主要驱动力。当温度升至230-310°C时,电解液溶剂发生剧烈热分解,产生CO和CO3,进一步加速系统向高温状态的演进。最终在270°C至370°C温度区间,阴极活性材料发生分解,释放活性氧物种。与此同时,PVDF粘结剂参与反应,不仅释放大量热量,还会产生氢氟酸(HF)等剧毒腐蚀性气体。活性氧物种会迅速氧化积聚的可燃气体,从而形成极高的着火或爆炸风险[6,23,24]。6O3, and C4H8O3. Unsaturated hydrocarbons constituted a significantly higher proportion of thermal runaway gases in 100 % SOC batteries compared to those at lower SOC levels. As shown in Table 1, this process begins with the thermal decomposition of the solid electrolyte interphase (SEI) film at low temperatures (80–120 °C). This reaction not only produces alkane gases but, more critically, disrupts the passivation layer on the negative electrode, creating conditions for subsequent intense exothermic reactions. Subsequently, within the 90–250 °C temperature range, the exposed lithiated anode undergoes vigorous reduction reactions with the electrolyte, generating considerable amounts of combustible gases such as hydrogen (H2), ethylene (C2H4), and carbon monoxide (CO), while releasing substantial heat. This becomes the primary driver of the system's temperature rise. As temperatures rise to 230–310 °C, the electrolyte solvent undergoes extensive thermal decomposition, producing gases like CO and CO2, further accelerating the system's progression to high-temperature states. Ultimately, at temperatures between 270 °C and 370 °C, the cathode active material decomposes, releasing reactive oxygen species. Concurrently, the PVDF binder participates in the reaction, not only releasing substantial heat, but also generating highly toxic and corrosive gases such as hydrogen fluoride (HF). The reactive oxygen species rapidly oxidize the accumulated combustible gases, creating a high risk of ignition or explosion [6,23,24]. During lithium battery TR, the ejection of high-temperature, high-pressure gases and particulate matter poses significant safety risks, potentially triggering fires or even explosions. In studies of single-cell TR, Feng et al. [28] proposed three characteristic temperatures of the thermal runaway process, establishing them as key common features for investigating battery thermodynamic responses. Furthermore, Feng et al. [29] sought to elucidate the underlying mechanisms of these three characteristic temperatures based on common patterns observed in battery databases. Their findings indicate that for batteries employing Li(NixCoyMnz)O2 cathodes and carbon-based anodes, the primary heat source during thermal runaway stems from redox reactions at high temperatures within the cathode and anode, while internal short circuits contribute minimally to the thermal runaway process. Some researchers have also investigated the gas evolution characteristics during battery thermal runaway. Studies have shown that TR gas evolution in lithium-ion batteries (LIBs) primarily consists of CO, CO2, H2, and short-chain olefins and alkanes [30,31]. Shen et al. [32] investigated in-situ gas generation during thermal runaway in different NCM and LFP batteries. Results indicate that LFP batteries produce a higher proportion of hydrogen gas during thermal runaway, resulting in less flammable thermal runaway gases compared to the mixed gases generated by nickel-magnesium-iron lithium batteries. Qi et al. [33] analyzed and risk-assessed the adiabatic temperature, gas composition, and flammability limits of commercial LiNi0.5Co0.2Mn0.3O2 lithium-ion batteries at different SOCs (50 %, 75 %, 100 %, 115 %). Results indicate that batteries at lower SOC exhibit lower TTR and Tmax values than those at higher SOC. As SOC decreases, gas generation diminishes. With increasing SOC, the lower flammability limit decreases while the upper limit increases. The highest hazard occurs at SOC = 115 %, while optimal safety is achieved at SOC = 50 %. Zhang et al. [22] conducted thermal runaway experiments on 18650 cylindrical lithium-ion batteries at different SOC levels, analyzing gas composition and explosion limits. Results indicate that as SOC increases, the variety of generated gases expands. The lower explosive limit (LEL) trend aligns with alkane content (initial rise followed by decline), while the upper explosive limit (UEL) trend correlates with unsaturated hydrocarbon content (first decreasing then increasing). A SOC of 50 % can serve as the safe storage threshold for lithium batteries. 热失控射流具有高温与能量集中的特性,这使其成为能量流分析中的关键要素。现有关于热失控能量流分析的研究主要基于稳态假设,难以捕捉热失控射流过程的动态特征。传热计算则主要依赖热阻法和固定传热系数假设。基于热阻法的对流热通量计算通常需要借助总热量等其他分量的间接推算,难以独立求解。Li等[34]研究了不同正极材料锂离子电池的热失控传播特性,采用热阻(δ/λ)计算热流密度时发现,三种电池中对流传热占比均为0.5%~0.8%。热失控过程中释放的总能量约90%通过自加热和排放损耗消散,而仅需约10%的释放能量即可触发失控传播。Wang等[35]研究了从单体电池到电池包系统的热失控传播(TRP)现象,同样采用热阻法计算热流密度,其对流换热贡献率约为0.7%。根据泄漏物质的物理化学特性,估算泄漏导致的能量损失约占总能量的31%。Li等[36]研究了侧板对热失控传播特性的影响,通过散热曲线获得TRP模块不同位置的对流换热系数,其值分别为15、15和5 W·m−2分别对应于顶部、侧面和底部的表面。他们的研究结果表明,在热失控传播过程中,侧板对传热路径和能量流分布具有显著影响。与无侧板的锂离子电池组相比,热失控单体释放的热通量会从前端界面向侧面转移,约40.8%的溢出能量通过侧板传递至相邻单体。Lai等学者[37]通过实验与计算分析,对比了锂离子电池模块在三种典型热扳机模式(加热扳机、针刺扳机与过充扳机)下的热响应行为。研究将表面对流换热系数分别设定为10、8、1和10 W·m−1分别通过实验数据进行了校准。研究发现,不同扳机模式仅影响热失控起始阶段的特征。能量通量分析表明,超过60%的热失控热量被电池自热消耗,约1%通过电池外壳以辐射和对流形式散失至周围空气中,26.5%由喷射物(如固体颗粒和烟雾)带走。值得注意的是,上述研究中涉及的对流换热系数计算与能量通量分析均基于稳态假设。−2 K−1, respectively, and calibrated using experimental data. Findings revealed that different trigger modes only affect the characteristics at the onset of thermal runaway. Energy flux analysis indicates that over 60 % of TR heat is consumed by battery self-heating, approximately 1 % is radiated and convected through the battery casing to the ambient air, and 26.5 % is removed by ejecta (e.g., solid particles and smoke). Notably, in the aforementioned studies, calculations of convective heat transfer coefficients and energy flux analysis in the aforementioned studies are all based on steady-state assumptions. 燃料费流速通过调节电池表面热边界层特性,成为对流传热强度的核心控制因素。Zou等[38]开发了一种基于电池内部压力预测喷射速度的方法,将电池热失控喷射过程划分为四个阶段。他们利用高速数码相机在第一阶段捕捉到两股喷射流,出口流速分别约为55和40米/秒,而第三阶段的平均固体颗粒流速达到8.3米/秒。Zhang等[39]提出了锂电池喷射指数KLIB基于爆炸指数(Kst并将其应用于锂离子电池喷射过程的定量分析。研究者将电池喷射过程划分为超快速、快速和慢速三个阶段。Li等[40]采用52Ah三元锂离子电池开展了热失控喷射实验,在8.012秒时测得峰值总喷射速度达210.86米·秒−1。他们首次利用卡门涡街技术成功区分了颗粒温度与燃料费温度,并推导出喷射动力学的经验方程。Mao等[41]研究了18650电池,根据产气速率将热失控气体生成划分为四个阶段。他们观察到燃料费生成速率与锂离子电池热失控期间的温升速率成正比。综合来看,这些研究表明电池喷射行为在流速方面表现出显著的极端性。由于流速与电池对流换热能力密切相关,需要进一步研究其对对流换热和动态能量流分析的影响。此外,荷电状态(SOC)影响能量通量和喷射动力学的机理仍不明确。 为研究热失控喷射过程中对流传热与能量流动的动态特性并阐明荷电状态(SOC)的影响机制,本研究搭建了热失控实验平台,针对商用锂离子电池在不同SOC条件下开展热失控实验。通过将喷射速度与对流传热系数相耦合,揭示了能量流输运的动态演化规律及其SOC依赖性特征。实验过程中同步记录了电池正极、负极及安全阀的表面温度,以及腔体温度与压力数据。采用气相色谱仪对热失控气体组分进行定量分析,基于理想气体状态方程计算气体流速,并将喷射过程划分为层流、过渡流和湍流三个阶段。在此基础上,利用半经验对流传热关联式计算努塞尔数。通过引入混合气体的物性参数,我们对对流换热系数的动态变化进行了分析。这建立了一种适用于电池热失控过程的动态能量传递分析方法,系统性地研究了荷电状态(SOC)对喷射特性及动态能量通量分布的影响机制。最终基于上述研究数据,构建了不同SOC条件下电池热失控的风险评估体系。