Lithium-ion energy storage battery explosion incidents

Utility-scale lithium-ion energy storage batteries are being installed at an accelerating rate in many parts of the world. Some of these batteries have experienced troubling fires and explosions. There have been two types of explosions; flammable gas explosions due to gases generated in battery thermal runaways, and electrical arc explosions leading to structural failure of battery electrical enclosures. The thermal runaway gas explosion scenarios, which can be initiated by various electrical faults, can be either prompt ignitions soon after a large flammable gas mixture is formed, or delayed ignitions associated with late entry of air and/or loss of gaseous fire suppression agent. The electrical explosions have entailed inadequate electrical protection to prevent high energy arcs within electrical boxes vulnerable to arc induced high pressures and thermal loads. Estimates of both deflagration pressures and arc explosion pressures are described along with their incident implications.     

A review of hazards associated with primary lithium and lithium-ion batteries

Primary lithium batteries contain hazardous materials such as lithium metal and flammable solvents, which can lead to exothermic activity and runaway reactions above a defined temperature. Lithium-ion batteries operating outside the safe envelope can also lead to formation of lithium metal and thermal runaway. Despite protection by battery safety mechanisms, fires originating from primary lithium and lithium-ion batteries are a relatively frequent occurrence.This paper reviews the hazards associated with primary lithium and lithium-ion cells, with an emphasis on the role played by chemistry at individual cell level. Safety mechanisms to prevent the occurrence and limit the consequences of incidents are reviewed, together with safety tests to monitor compliance with battery safety regulations and standards. Incident information from news accounts and open literature sources are reviewed to extract causal information.It is concluded that the potential severity of incidents during storage, transport and recycling of waste batteries can be significantly higher than in end-use applications. Safe storage, packaging and labelling practices, as well as communication among the parties involved, are essential to ensure safety across the battery lifecycle. It is recommended that a database of lithium battery incidents would be valuable to improve the evidence base for informing accident prevention measures.     

Lower explosion limit of the vented gases from Li-ion batteries thermal runaway in high temperature condition

The thermal runaway of lithium-ion battery (or Li-ion battery, LIB) results in scrap of battery and fire, with the toxic and flammable gases generated. In this work, a self-made device was to collect gases from LIB thermal runaway, when the batteries were under different states of charge (SOC), temperatures of the environment and powers of external heating. Three samples of the collected gases were analyzed to get the results of the composition and content by chromatography-mass spectrometry system (GC-MS). The lower explosion limits (LELs) of the gases was tested by FRTA explosion limit instrument. And then the LEL of three analyzed samples whose composition and content were known by GC-MS were calculated via theoretical formulas. The calculated LELs were compared with those of the instrument test. The errors of the two results of three samples are 2.1%, 1.9%, and 0.4%. The Le Chatelier Formula and empirical formula provide a way to evaluate the LEL of the battery runaway gas more quickly.     

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...     

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。     

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。     

Does your facility have a dust problem: Methods for evaluating dust explosion hazards

The hazards of dust explosions prevailing in plants are dependent on a large variety of factors that include process parameters, such as pressure, temperature and flow characteristics, as well as equipment properties, such as geometry layout, the presence of moving elements, dust explosion characteristics and mitigating measures. A good dust explosion risk assessment is a thorough method involving the identification of all hazards, their probability of occurrence and the severity of potential consequences. The consequences of dust explosions are described as consequences for personnel and equipment, taking into account consequences of both primary and secondary events.While certain standards cover all the basic elements of explosion prevention and protection, systematic risk assessments and area classifications are obligatory in Europe, as required by EU ATEX and Seveso II directives. In the United States, NFPA 654 requires that the design of the fire and explosion safety provisions shall be based on a process hazard analysis of the facility, process, and the associated fire or explosion hazards. In this paper, we will demonstrate how applying such techniques as SCRAM (short-cut risk analysis method) can help identify potentially hazardous conditions and provide valuable assistance in reducing high-risk areas. The likelihood of a dust explosion is based on the ignition probability and the probability of flammable dust clouds arising. While all possible ignition sources are reviewed, the most important ones include open flames, mechanical sparks, hot surfaces, electric equipment, smoldering combustion (self-ignition) and electrostatic sparks and discharges. The probability of dust clouds arising is closely related to both process and dust dispersion properties.Factors determining the consequences of dust explosions include how frequently personnel are present, the equipment strength, implemented consequence-reducing measures and housekeeping, as risk assessment techniques demonstrate the importance of good housekeeping especially due to the enormous consequences of secondary dust explosions (despite their relatively low probability). The ignitibility and explosibility of the potential dust clouds also play a crucial role in determining the overall risk.Classes describe both the likelihood of dust explosions and their consequences, ranging from low probabilities and limited local damage, to high probability of occurrence and catastrophic damage. Acceptance criteria are determined based on the likelihood and consequence of the events. The risk assessment techniques also allow for choosing adequate risk reducing measures: both preventive and protective. Techniques for mitigating identified explosions risks include the following: bursting disks and quenching tubes, explosion suppression systems, explosion isolating systems, inerting techniques and temperature control. Advanced CFD tools (DESC) can be used to not only assess dust explosion hazards, but also provide valuable insight into protective measures, including suppression and venting.     

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。     

Case study: T2 Laboratories explosion

A tragic explosion resulting from a runaway chemical reaction occurred at the T2 Laboratories, Inc. facility in December 2007. The U.S. Chemical Safety Board (CSB) completed an incident investigation of the T2 explosion, identifying the root cause as a failure to recognize the runaway reaction hazard associated with the chemical it was producing. Understanding the consequences of process upset conditions is critical to determine risk. This paper will focus on lessons learned from this incident including a comprehensive hazard assessment for reactive chemicals as well as proper collection and application of adiabatic calorimetry data to characterize the chemical reaction and determine appropriate mitigation strategies. Examples will be provided to establish safer operating conditions, implement safeguards and reduce the overall risk.     

A quantitative risk management framework for dust and hybrid mixture explosions

Dust and hybrid-mixture explosions continue to occur in industrial processes that handle fine powders and flammable gases. Considerable research is therefore conducted throughout the world with the objective of both preventing the occurrence and mitigating the consequences of such events. In the current work, research has been undertaken to help move the field of dust explosion prevention and mitigation from its current emphasis on hazards (with an accompanying reliance on primarily engineered safety features) to a focus on risk (with an accompanying reliance on hierarchical, risk-based, decision-making tools). Employing the principles of quantitative risk assessment (QRA) of dust and hybrid-mixture explosions, a methodological framework for the management of these risks has been developed.The QRA framework is based on hazard identification via credible accident scenarios for dust explosions, followed by probabilistic fault-tree analysis (using Relex – Reliability Excellence – software) and consequence severity analysis (using DESC – Dust Explosion Simulation Code – software). Identification of risk reduction measures in the framework is accomplished in a hierarchical manner by considering inherent safety measures, passive and active engineered devices, and procedural measures (in that order). An industrial case study is presented to show how inherent safety measures such as dust minimization and dust/process moderation can be helpful in reducing dust and hybrid-mixture explosion consequences in a 400-m³ polyethylene storage silo.     

低压环境下不同三元圆柱锂电池热失控危险特性对比研究

为研究21700和18650新旧2型多用途锂离子电池在航空运输低压环境下的热失控特性差异，采用动压变温实验舱搭建实验平台开展实验。将实验环境压力设定为飞机巡航时的环境压力30 kPa，对比常压101 kPa，使用外部热源加热的方式触发锂电池热失控，利用热传播引发相邻电池热失控，分别从热失控温度变化特性、热释放速率和热解气体组分浓度变化进行分析。研究结果表明:能量密度更高的21700电池热失控峰值温度更高，高温危险性要高于18650电池，但触发热失控所需的热量更多，电池间热传播时间会延长；低压环境有利于降低锂电池热失控燃爆峰值温度，减小燃爆热释放速率，但会产生更多CxHy和CO等具有燃爆性的热解气体，可能会在有限空间内与氧气混合引起二次燃爆。     

反应失控型火灾爆炸事故预测

介绍了一种预测反庆失控灾害的方法,通过实验测定容器的时间常数,预测能够引起反应失控的最低环境温度,发生反应失控时的危险温度,以及达到最大反应速度反需的时间,预测结果与实际情况具有良好的一致性。     

Applications of dust explosion hazard and disaster prevention technology

Powdered materials are widely used in industrial processes, chemical processing, and nanoscience. Because most flammable powders and chemicals are not pure substances, their flammability and self-heating characteristics cannot be accurately identified using safety data sheets. Therefore, site staff can easily underestimate the risks they pose. Flammable dust accidents are frequent and force industrial process managers to pay attention to the characteristics of flammable powders and create inherently safer designs.This study verified that although the flammable powders used by petrochemical plants have been tested, some powders have different minimum ignition energies (MIEs) before and after drying, whereas some of the powders are released of flammable gases. These hazard characteristics are usually neglected, leading to the neglect of preventive parameters for fires and explosions, such as dust particle size specified by NFPA-654, MIE, the minimum ignition temperature of the dust cloud, the minimum ignition temperature of the dust layer, and limiting oxygen concentration. Unless these parameters are fully integrated into process hazard analysis and process safety management, the risks cannot be fully identified, and the reliability of process hazard analysis cannot be improved to facilitate the development of appropriate countermeasures. Preventing the underestimation of process risk severity due to the fire and explosion parameters of unknown flammable dusts and overestimation of existing safety measures is crucial for effective accident prevention.     

锂电池检测的安全标准及安全防护研究

为评估并提高锂电池在使用、储存和运输过程中的安全,本文归纳总结了国内外锂电池安全检测的相关标准,对标准中测试项目异同作了重点分析和对比,并讨论了锂电池的安全风险及风险分级情况。同时,鉴于锂电池检测过程中可能出现的起火、爆炸等危险,探讨了电池检测过程的安全防护技术,并从样品区和试验区两方面提出了安全防护要求和建议。     

锂离子电池组热失控蔓延热传递机制的影响研究

分析通风和电池组数量对电池组热失控发展蔓延热传递机制的影响。选择荷电状态(SOC)为100%的镍钴锰(NCM523)三元锂离子动力电池组作为研究对象,改变电池组底部外加热源的热流量和加热时间,利用多物理场仿真软件COMSOL,进行热滥用导致不同风速通风环境和不同电池数量电池组热失控过程的模拟。结果表明:随着风速不断增大,电池组和周围环境的对流换热损失增强,电池组热失控蔓延进程受到了有效抑制。受热传导模式的影响,电池组数量和排列方式不同,电池组热失控蔓延的路线不同。越靠近外部热源的电池,触发热失控越早,触发热失控的起始温度越高;电池组所含电池数量越多,触发电池组热失控所需的热流量越大,但第一块电池热失控以后,后续电池触发热失控的时间间隔急剧缩短,电池组热失控后果的严重度增加。     

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,但是各阶段的特性却存在差异。池体表面中心温度、HRR,THR和耗氧量均随外热功率的降低而降低。高外热功率下燃爆响应时间点明显提前,池体温度更高,220 W外热功率下,燃爆响时间点为176 s,池体温度为720.6 ℃,比70 W时提前366 s,高210.03 ℃,可见高外热功率时,电池热危害性更高。热解烟气CO的峰值体积百分比浓度随着外热功率的降低而升高,而CxHy的峰值质量百分比浓度降低,,CO2的峰值体积百分比浓度降低。在70 W外热功率时,CO峰值体积百分比浓度高达0.322%,220 W时CO峰值体积百分比浓度仅为0.165%,说明低外热功率时,电池毒危害性更高。     

易燃液体仓库安全监控系统研究

通过对易燃液体仓库的潜在危险的分析和研究,以及火灾爆炸危险性分析,说明安全监控技术的重要性。在对监测参数进行分析的基础上,给出了对监测易燃液体仓库的安全监控系统和监测点的布置以及采用合适的探测器。     

可燃气体储罐区泄漏危险性定量分析

对位于某城市中心附近的可燃气体储罐区的气体泄漏危险性进行了分析,求出了下风向最大可燃范围和中毒范围.进行灵敏度分析以便识别风速、泄漏面积对泄漏危险性的影响.分析结果显示,风速、泄漏面积对泄漏危险性有显著影响.随着泄漏面积增大,下风向最大可燃范围增大;随着风速的增大,下风向最大可燃范围则减小.最后提出了若干安全措施的建议.