Causes and consequences of thermal runaway incidents—Will they ever be avoided?

A study of runaway incidents involving thermal chemical reactions in the UK over the past 25 years (1988–2013) has been carried out. The objective of this study is to determine possible causes of thermal runaway incidents. A statistical analysis of the underlying problems that led to thermal runaway incidents has been provided. A comparison of the current study on thermal runaway incidents with those identified prior to 1988 has been carried out. This study clearly shows that lessons have not been learnt from thermal runaway incidents caused by operator errors, management failures and lack of organised operating procedures. These factors have been the possible causes of about 77% of all the thermal runaway incidents analysed in this study. The number of fatalities and injuries as a result of thermal runaway incidents has increased by ∼325% and ∼279%, respectively, in the last 25 years even though the number of incidents was significantly less. On the basis of this analysis, several recommendations have been proposed that could help to minimise the risks associated with any thermal runaway incidents in the future.     

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.     

Parametric sensitivity analysis for thermal runaway in semi-batch reactors: Application to cyclohexanone peroxide reactions

The semi-batch reactors (SBRs) system, which is widely used in industrial processes, possesses an intrinsic parametric sensitivity, in which infinitesimal disturbances of input parameters can result in large variations in output variables. In this work, local parametric sensitivity analysis (PSA) was used to understand parameter variations and global PSA was conducted to examine the interaction of input parameters. The effects of these parameters on the output of the system model were analyzed based on the Monte Carlo method with Latin hypercube sampling and the extended Fourier amplitude sensitivity test model. The results showed that the evolution of thermal behaviors in SBRs were observed: marginal ignition; thermal runaway; and the quick onset, fair conversion, and smooth temperature profile. The threshold point of transition from marginal ignition to thermal runaway was at the maximal value of local sensitivity, for which the slope with respect to cooling temperature equaled zero. Moreover, the sequence of the global sensitivity of six common input parameters was computed and evaluated. The reliability of the numerical models was verified by using our previous experimental results of cyclohexanone peroxide reaction. This comprehensive sensitivity analysis could provide valuable operating information to improve chemical process safety.     

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。     

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.     

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。     

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.     

An incident investigation on an unexpected loss of containment and damage to PHI-TEC II during acrylonitrile runaway tests

This article investigates a laboratory incident that occurred during the analysis of a thermal runaway reaction of acrylonitrile monomer. This failure, which was attributed to an human error, resulted in financial losses and corresponding unexpected results. The incident not only damaged the interior of the vessel and other instrument parts, but also exposed the researchers to considerable danger, necessitating their escape from the laboratory. The failure characteristics are discussed, and countermeasures are developed to prevent such a type of incident from reoccurring.     

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。     

Applications of thermal hazard analyses on process safety assessments

In 2011, a large petrochemical complex in Taiwan incurred several fire and explosion accidents, which had considerable negative impact for the industry on both environmental and safety issues. Reactive substances are widely used in many chemical industrial fields as an initiator, hardeners, or cross-linking agents of radical polymerization process with unsaturated monomer. However, the unpredictable factors during the process having risk to runaway reaction, thermal explosion, fire, and exposure to harmful toxic chemicals release due to the huge heat and gas products by thermal decomposition could not be removed from the process. This study used differential technology of thermal analysis to characterize the inherent hazard behaviors of azo compounds and organic peroxides in the process, to seek the elimination of the source of the harmful effects and achieve the best process safety practices with zero disaster and sound business continuity plan.     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

Using thermal analysis with kinetic calculation method to assess the thermal stability of azo compound on construction materials

The application of construction polymers in engineering and alternative materials has always occupied a place in the market. In the production process of polymer resins, initiators can be used to lower the polymerization reaction energy threshold, which can improve reaction efficiency and reduce energy loss. However, as a commonly used energetic substance in the polymerization process, azos have caused related process hazards due to their exothermic characteristics. Because of this, it is essential to examine and analyze the thermal hazard characteristics of emerging azo substances, such as 2-cyanopropan-2-imemicarbazide (CABN). Although previous literature performs the calculation on related thermal hazard parameters of CABN, there is still exists a void for discussion in estimating the reaction model to avoid analogous hazards and enhance the existing thermal analysis. Based on the past literature, the reaction model is improved with thermogravimetric analysis as evidence. The revised thermal hazard parameters are calculated as the basis of control and mitigation measures, the kinetic model is used to estimate the modified safety parameters, and in the judgment of the runaway reaction, the critical temperature of the runaway is found by analyzing the influence of slight changes in ambient temperature on the reaction temperature. The results show that the critical temperature that causes CABN to enter the runaway reaction is delayed, and the hazard is lower than in the storage situation. Therefore, the thermal hazard to CABN mainly focuses on the safety environment and measures during storage.     

Guidance to improve the effectiveness of process safety management systems in operating facilities

The Process Safety Management (PSM) systems at the operating facilities in the Oil & Gas and in Chemical manufacturing industries have matured over the years and have become, at most facilities, very robust and sophisticated. These programs are administrated by Process Safety (PS) teams at both the corporate business units and plant levels and have been effective in reducing the number and severity of PS events across the industries over the past 25 years or so. Incidents however are occurring at a regular interval and in recent times several noteworthy PS events have occurred in the United States which have brought into question the effectiveness of the PSM programs at play. These facilities have been applying their PSM programs with the expectation that the number and severity of PS events would decrease over time. The expected result has not been realized, especially in context to those facilities that have undergone the recent incidents. Current paper reviews a few publicly available PS performance reports of Oil & Gas and Chemical manufacturing industries. The authors identified a few factors at play that have led to these PS events based on their experience, literature review, and incident investigation reports. Most of the factors are intertwined with multiple PSM elements and it requires a holistic approach to address them. Each of the factors is described and the path forward is proposed to improve the effectiveness of PSM programs.     

Effects of thermal radiation heat transfer on flame acceleration and transition to detonation in particle-cloud hydrogen flames

The current work examines regimes of the hydrogen–oxygen flame propagation and ignition of mixtures heated by radiation emitted from the flame. The gaseous phase is assumed to be transparent for the radiation, while the suspended particles of the dust cloud ahead of the flame absorb and reemit the radiation. The radiant heat absorbed by the particles is then lost by conduction to the surrounding unreacted gaseous phase so that the gas phase temperature lags that of the particles. The direct numerical simulations solve the full system of two phase gas dynamic time-dependent equations with a detailed chemical kinetics for a plane flames propagating through a dust cloud. It is shown that depending on the spatial distribution of the dispersed particles and on the value of radiation absorption length the consequence of the radiative preheating of the mixture ahead of the flame can be either the increase of the flame velocity for uniformly dispersed particles or ignition either new deflagration or detonation ahead of the original flame via the Zel'dovich gradient mechanism in the case of a layered particle-gas cloud deposits. In the latter case the ignited combustion regime depends on the radiation absorption length and correspondingly on the steepness of the formed temperature gradient in the preignition zone that can be treated independently of the primary flame. The impact of radiation heat transfer in a particle-laden flame is of paramount importance for better risk assessment and represents a route for understanding of dust explosion origin.