太空环境下锂离子电池热失控与火灾的研究展望

综述了锂离子电池的热失控机理,介绍了由于电池内部电解液、电池隔膜和电极材料分解的链式热反应过程而引发的热失控和火灾现象。同时,讨论了锂离子电池在微重力太空环境中可能产生的烟黑浓度倍增,加速火蔓延,火焰喷射等极端火行为。进而探讨了开展锂离子电池的低压、落塔和抛物飞行等地面实验模拟太空微重力燃烧的方法可行性,建立数值模型预测太空微重力环境下锂离子电池热失控临界条件与火灾行为的必要性,以及如何通过基础研究科学地指导空间站电池热管理和消防系统的设计。     

基于火探管式的锂离子电池灭火技术研究

为研究锂离子电池灭火方案,基于火探管灭火技术同时利用新型清洁灭火剂Novec 1230,组装成火探管灭火系统。在灭火测试平台上以功率为200 W的电热管作为外热源引发单电池或电池模组热失控,通过改变火探管的布置位置,记录相应的灭火行为以及灭火效率,并对实验结果进行了分析。研究结果表明,当火探管灭火系统直接布置在电池正上方时,在起火后的5.6s内控制火情;随着灭火剂用量增加可以显著降低体系温度,防止电池复燃以及连锁热失控现象发生;火探管有效覆盖区域外的失控电池作为热源将继续加热临近电池,引发连锁热失控,造成灭火系统失效;根据电池热失控后的燃烧行为以及传热行为,提出相应的火探管灭火系统复合方案。     

Effects of environmental temperature on the thermal runaway of lithium-ion batteries during charging process

Lithium-ion batteries with relatively narrow operating temperature range have provoked concerns regarding the safety of LIBs. In this work, a series of experiments were conducted to explore the thermal runaway (TR) behaviors of charging batteries in a high/low temperature test chamber. The effects of charging rates (0.5 C, 1 C, 2 C, and 3 C), and ambient temperature (2 °C, 32 °C and 56 °C) are comprehensively investigated.The results indicate that the cell exhibited greater thermal hazard at the high charging rate and ambient temperature conditions. As the charging rate increased from 0.5 C to 3 C, more lithium intercalated in the anode prompt the TR triggered in advance, the TR onset temperature decreased from 297.5 °C to 264.7 °C. In addition, the charging time decreased with the elevated ambient temperature, resulting in a relatively higher TR onset temperature and lower maximum temperature, and the average TR critical time declined by 115–143 s. Finally, the TR required less heat accumulation with increasing of charging rate and ambient temperature, and the heat generation of side reaction played a substantial role that accounted for approximately 54%∼63%. These results provide an insight into the charging cell thermal runaway behaviors in complex operation environments and deliver valuable guidance for improving the safety of cell operation.     

模组箱体空间内磷酸铁锂电池热失控及其传播行为研究

为了探究储能用锂离子电池在真实应用场景下的热失控及其传播行为特征,选用86 Ah方形磷酸铁锂(LiFePO₄)电池,对其在热滥用触发方式下的热失控行为及模组箱体空间与开放空间中的传播行为规律进行了实验研究。单体实验结果表明,电池热失控产生的高温烟气会导致模组箱体内沿高度方向出现明显温度梯度,模组底部与顶部温度测点的最大温差达118.4℃。传播实验结果表明,模组箱体空间内热失控电池通过产气及喷出高温电解液向其他电池传热,在热失控电池影响下,模组箱体空间内3块电池上表面所能达到的最高温度均高于开放空间实验12℃～150℃,模组空间内热失控电池向同侧两块电池的传热量高于开放空间实验225 kJ和44.4 kJ。但箱体环境中有限的氧气供给会减缓电池在热失控时的内部放热反应进程,模组箱体空间实验中电池热失控峰值温度较开放空间实验低33℃～145℃,并且模组箱体空间实验中热失控完全传播所用时间较开放空间实验滞后213 s。研究结果对于锂离子电池模组的安全设计和热失控传播阻隔具有一定的参考价值与指导意义。     

细水雾对锂离子电池热失控抑制作用的实验研究

为研究细水雾对锂离子电池热失控的抑制作用,利用自设计细水雾实验装置对18650型锂离子电池热失控进行抑制实验,对比两节电池依次燃爆和不同阶段使用细水雾的温度曲线。研究表明,细水雾对于抑制锂离子电池热失控有效,但不同热失控阶段细水雾抑温效果差异较大,结合锂离子电池多米诺效应和机载灭火设备适航性要求,应尽可能将细水雾喷雾时间节点靠近初次爆炸的时间节点。提出通过准确探测初次爆炸发生和进一步增强细水雾抑制作用来控制锂离子电池热失控及多米诺效应的发生和传播。     

Experimental study on thermal runaway risk of 18650 lithium ion battery under side-heating condition

To simulate the heat transfer process between lithium-ion batteries (LIBs), an electric heater with the same size and shape as LIB in this work is used to trigger thermal runaway event. The effect of state of charge (SOC), the power of heater, the cell spacing on thermal behavior of LIB was investigated as well the amount of transferred heat between the heater and LIB was calculated. The results indicate that 50% SOC is an unstable state for LIB, that a stronger jet flame becomes more likely when the SOC of LIB is higher than 50%. Additionally, the increased spacing, lower heating power and SOC can contribute to mitigate the severity of thermal runaway behavior. Further, the dominant path of heat transfer between the heater and LIB will also vary with operating conditions. The heat conduction through air is the main heat transfer path in tests with lower heating power. However, heat radiation will replace heat conduction as the primary heat transfer mode when there is a large temperature difference between the heater and LIB in tests with higher heating power. Understanding the leading heat transfer path between LIBs can provide valuable guidelines for the safety design of lithium-ion battery modules.     

细水雾抑制18650型锂离子电池热失控实验研究

为研究细水雾灭火系统对18650型锂电池热失控的抑制效果,利用自设计实验平台进行抑爆实验,对比初爆与燃爆两个关键点及有无外部热源的温度变化图。研究表明,细水雾能够明显抑制18650型锂电池热失控,但施加细水雾的时间点对抑制效果影响较大,初爆后施加细水雾能够有效抑制,在燃爆后施加细水雾10s内温度降低200℃以上,但由于锂电池内部电解液复燃的特点,温度回升。温升速率的变化使得电池初爆的时间和温度分别提前了67.4%和44.4%,据此提出通过探测18650型锂电池初爆释放气体发现热失控发生并在最短时间内移除异常行为电池来控制电池热失控及其热量的异常传播。     

常压及低压下锂电池热失控随数量变化特性

为明确在地面常压环境和商用飞机巡航高度低气压环境下锂电池热失控火灾危险特性随电池数量的变化关系,分别于95 kPa地面常压环境和20 kPa低压环境下,开展不同电池数量梯度的热失控试验,测量热释放速率,总热释放量,烟气温度,CO、CO2和碳氢等气体的实时体积分数.结果表明:最高热释放速率和总热释放量与电池数量均呈幂函数...     

不同外热部位下18650型锂离子电池热失控研究

为探究不同外热部位对18650型锂离子电池热失控特性的影响,通过自主设计的试验平台对电荷量为100%的18650型锂离子电池开展不同外热部位下热失控试验,探讨不同部位外热源对电池热失控行为过程、热失控响应时间、温度特性、电池破裂部位的影响。结果表明:在相同热源功率条件下,外热源位置对电池热失控过程中初爆与二次燃爆间的时间间隔存在影响,顶部加热时安全阀打开瞬间便发生二次燃爆,底部和中部加热工况下,时间间隔分别延迟至18 s和40 s;中部加热时池体温升速率最慢,为0.873℃/s,分别为顶部和底部加热时的77.5%和77.8%;中部加热时热失控响应时间最长达290 s,顶部和底部加热时分别缩短12.4%和30.0%;顶部和底部加热时,热失控破裂部位集中于顶部"褶皱处"和底部防爆阀,但在中部加热工况下,电池发生破裂部位的随机性增加,其外壳破坏程度也有增加。     

Micro calorimeter study on the thermal stability of lithium-ion battery electrolytes

With the extensive applications of lithium-ion batteries, many batteries explosion accidents were reported. The thermal stability of lithium-ion battery electrolyte could substantially affect the safety of lithium-ion battery. The C80 micro calorimeter was used to study the thermal stability of several commonly used organic solvents and electrolytes. The samples were heated in argon atmosphere and air atmosphere, respectively. The chemical reaction kinetics was supposed to fit by an Arrhenius law, then the self-accelerating decomposition temperature was calculated. It is found that most of the samples are stable in argon atmosphere while decomposing in air atmosphere, and the single organic solvent is more stable than the electrolyte generally.     

Inherent thermal runaway hazard evaluation method of chemical process based on fire and explosion index

Thermal runaway hazard assessment provides the basis for comparing the hazard levels of different chemical processes. To make an overall evaluation, hazard of materials and reactions should be considered. However, most existing methods didn't take the both into account simultaneously, which may lead the assessment to a deviation from the actual hazard. Therefore, an integrated approach called Inherent Thermal-runaway Hazard Index (ITHI) was developed in this paper. Similar to Dow Fire and Explosion Index(F&EI) function, thermal runaway hazard of chemical process in ITHI was the product of material factor (MF) and risk index (RI) of reaction. MF was an indicator of material thermal hazards, which can be determined by initial reaction temperature and maximum power density. RI, which was the product of probability and severity, indicated the risk of thermal runaway during the reaction stage. Time to maximum rate under adiabatic conditions and criticality classes of scenario were used to indicate the runaway probability of the chemical process. Adiabatic temperature rise and heat of the desired reaction and secondary reaction were used to determine the severity of runaway reaction. Finally, predefined hazard classification criteria was used to classify and interpret the results obtained by this method. Moreover, the method was validated by case studies.     

Thermal hazards analysis of styrene in contact with impurities

Styrene is a reactive monomer commonly used to produce polystyrene and other copolymers. Unintended thermal runaway polymerization reactions of styrene keep reoccurring and have led to catastrophic consequences. One of the possible causes of these runaway incidents involves the contamination of the styrene monomer by incompatible species, which was not adequately investigated and documented. This study focuses on the quantification of thermal runaway hazards of styrene in contact with a series of contamination substances by adopting calorimetric analysis. Both Differential Scanning Calorimeter (DSC) and Advanced Reactive System Screening Tool (ARSST) were employed to examine the exothermic characteristics of styrene mixed with contaminating substances at different concentration levels and mixing conditions. Key safety parameters of the exothermic reaction, such as the onset temperature, the overall heat release, the maximum self-heating rate, as well as the activation energy, were obtained. The results indicated that the thermal runaway polymerization of purified styrene was significantly altered by the presence of contaminant species. Water effectively retarded and quenched the runaway polymerization at a higher temperature range. Alkaline had no substantial effect on the thermal runaway characteristics. The presence of acid solution under both static contact and vigorous mixing condition significantly promoted the thermal polymerization of styrene. A trace amount of concentrated acid initiated violent exothermic activity even at room temperature; and the severity of the reaction was profoundly impacted by the mass-transfer. Our study demonstrates significant implications in the prevention of runaway incidents during transportation and storage of styrene.     

不同外热功率下18650锂离子电池热失控特性

为探究不同外热功率(220,170,120,70 W)下锂离子电池的热失控特性,采用动压变温实验舱作为燃爆实验舱,并利用量热仪和ISO-9705烟气分析仪监测特征参数,对荷电状态(SOC)为100％的18650型锂离子电池进行高温热失控实验.结果表明:在不同的外热功率条件下,锂离子电池进入热失控的过程呈现出相似的趋势,...     

航空压力环境对锂离子电池热解气体爆炸极限影响*

针对航空锂离子电池热失控释放气体安全性研究不足的问题,采用气体拉曼光谱技术、气相色谱仪(Gas Chromatography,GC)和质谱(Mass Spectroscopy,MS)耦合来探究压力和荷电状态(State of Charge,SOC)对锂离子电池早期故障气体类型、气体动态演变及气体潜在危险性等特征的影响规律,同时综合考虑压力、电压和电池温度等多种因素分析锂离子电池热失控危害。研究结果表明:电池SOC越高且环境压力越低,电池越早触发热失控,爆炸极限越宽,其中30 kPa下100%SOC电池热解气体爆炸极限为8.01%~53.35%;SOC和环境压力越高,电池热失控越危险,释放的气体体积越多;CO,CO2,PF3,C2H4及电解液（C3H6O2、C3H6O3、C4H8O2）等气体可作为航空锂离子电池早期故障诊断特征。研究结果对保障锂离子电池在航空领域的安全运输及应用具有重要意义。     

锂电池火灾灭火技术研究综述

为系统了解锂电池火灾灭火技术研究现状,综述国内外针对锂电池火灾的灭火实验研究,基于锂电池火灾的特点,从灭火效果、冷却效果和毒性危害等方面分析各类灭火剂对锂电池火灾的适用性,指出目前研究存在的问题以及今后的研究重点。研究结果表明：灭火剂的冷却能力是抑制锂电池内部链式分解反应,进而阻止锂电池复燃和热失控传播的关键因素。未来研究应更贴近实际工程应用,从灭火效率、冷却能力、毒性影响和有无不良抑制作用等角度综合评估灭火剂的有效性。     

钛酸锂电池在绝热环境中循环的热响应特性

钛酸锂电池广泛应用于储能系统,其安全性也备受关注。采用加速量热仪与电池循环仪联用技术,对钛酸锂电池在循环过程中的热响应情况进行了研究。研究表明,测试电池在放电和充电阶段均有明显的小幅度温升现象。通过测试电池在不同倍率下的产热情况,发现电池在各循环阶段的绝热产热量与循环倍率成正比,其热失控危险性也随着循环倍率的增大而增加。     

受限空间环境压力对三元锂离子电池热失控影响

为研究三元锂离子电池在空运低压环境中的安全性,通过自主设计搭建的封闭式变压实验舱开展相关实验,对不同荷电状态(SOC)下的三元锂离子电池在不同压力环境(101,80,60,40 kPa)下的热失控特性进行研究,采集电池热失控过程中的温度以及实验舱内的压力变化,并对热失控后实验舱内的气体成分进行分析.结果表明:三元锂离子...     

高温环境下18650型锂离子电池热失控过程的数值分析

采用ANSYS对高温条件下铜棒代替锂离子电池的空白试验进行数值模拟,获得拟合的陶瓷化纤棉毯的比热容;然后对18650型锂离子电池的热响应进行模拟,通过模拟结果与试验数据的比较分析,获得锂离子电池内部的反应放热量;最后应用得出的陶瓷化纤棉毯比热容和化学反应热对高温环境下18650型锂离子电池的热失控进行模拟,研究18650型锂离子电池热失控的变化规律.结果表明:20W加热条件下,锂离子电池的放热反应热为30 kJ;锂离子电池在加热1 287 s后发生热失控,热失控持续113 s后锂离子电池温度达最高,之后开始缓慢减小;锂离子电池热失控温度为500 K,热失控前温度几乎是线性增加,之后热失控导致温度迅速增加(呈指数倍增长);锂离子电池保温材料陶瓷化纤棉毯的温度变化是非线性的.     

低压环境对锂电池热失控释放温度影响

为研究锂电池在民航飞行低压特殊环境的安全性及发生热失控灾害后的高温危险性,通过可模拟飞行变动条件的动压变温实验舱开展系列实验,研究锂电池在不同低压环境下的（101,60,30 kPa）多节18650型锂离子电池热失控温度特性,采集电池池体温度及热失控喷射释放温度等参数。研究结果表明:随环境压力降低,圆柱锂电池间的热失控传播并不能被阻断,但锂电池热失控灾害所释放产生的高温区域减少,且高温持续时间变短,释放所产生温度的高温危险性随环境压力的降低而有所降低。     

Investigation on the self-decomposition and explosion hazard of azo compounds

Azo compounds are self-reactive chemicals that violently produce flammable gases with heat release (i.e., an exothermic reaction). However, the explosion mechanism and ignition probability of azo compounds have not been clearly defined for storage or transportation. In this study, explosion scene analyses and various pyrolysis tests were performed to evaluate the thermal decomposition characteristics and explosion phenomena of azo compounds in a storage facility. The chemical debris collected from a fire scene was determined to be similar to the pyrolyzate of one of the tested azo compounds used by Py-GCMS. The minimum amounts of azo compounds, which could be ignited by self-decomposition heat, were calculated from the results of differential scanning calorimetrys and the heat transfer equation. The results were used to discuss a safety and response strategy for preventing the propagation of an explosion accident, namely a chemical backdraft.