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。     

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。     

锂离子电池安全性特点及热模型研究

锂离子电池的安全问题越来越受到重视.本文从锂离子电池热安全性特点着手,分析了锂离子电池的着火、爆炸和电解液泄漏等安全事故特点.简单介绍了锂离子电池主要材料的产热特性、相互反应产热特性.讨论了锂离子电池热模型建立的两种途径,即量热仪途径和化学反应途径,通过这些热模型的建立,来指导锂离子电池的安全设计和管理.     

锂离子电池火灾危险性研究

为解决锂离子电池在应用、运输中的火灾安全问题,并为锂离子电池火灾扑灭技术研究提供支撑,以钴酸锂18650型及大容量的聚合物锂离子电池为研究对象,通过开展针刺、短路、耐热等滥用试验寻求锂离子电池及电池组引发火灾的条件和因素。通过开展燃烧试验,分析锂离子电池的燃烧特点。试验结果表明:正极材料为钴酸锂的18650型锂离子电池自燃温度约为170℃,大容量的聚合物锂离子电池组在内部短路后,可能发生燃烧甚至轰燃现象且燃烧残留物温度高,易引发火灾;18650型锂离子电池在短路条件下会长时间持续放热,存在引发火灾的可能;单只锂离子电池燃烧后能够引燃相邻的电池,从而形成电池组的连锁燃烧反应。     

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...     

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.     

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。     

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.     

包装性能对空运锂电池热失控影响的定量研究

包装是防止空运锂电池热失控后果扩大的关键,提出了一种基于试验的空运锂电池包装性能定量评价方法,利用自主设计的锂电池火灾试验平台对锂电池包装件开展热失控试验,结合试验结果分析选取初爆时间、初爆和燃爆时间间隔、热失控电池数量、峰值温度作为锂电池包装性能等级评价指标,引入物元可拓法构建包装性能熵权物元可拓模型,通过对不同包装形式和材料的锂电池包装件进行评价可知:现有瓦楞纸包装性能等级为Ⅲ(差),会严重威胁锂电池空运安全;采用玻璃纤维板包装,包装方式为玻璃纤维隔板加盖板时性能等级为I(优良),可显著提高空运安全性。     

不同环境体系下锂离子电池热失控特性实验研究

针对锂离子电池热失控引发的航空运输安全问题,自主设计并搭建锂离子电池热失控灾害演化及危险性分析实验平台。在敞开和密封环境体系下,对电加热触发荷电量(State of Charge,SOC)为0%、50%和100%的18650型锂离子电池热失控规律进行了实验研究。观察单体锂离子电池在敞开和密封体系中的热失控现象,并记录单体锂离子电池热失控时间、温度峰值及相应的温度变化。数据结果显示,相比敞开体系,密封体系有效的延缓了锂离子电池发生热失控的时间,并降低了锂离子热失控时释放的能量,为锂离子电池的航空运输安全性研究提供了理论依据和工程技术参考。     

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.     

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.     

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:三元锂离子电池热稳定性随着SOC的升高而下降,常压下100%SOC的电池热失控温度可达650.8 ℃,初始环境压力越低,相同SOC的电池热失控最高温度越低。随着环境压力的降低,相同SOC的电池在热失控后会生成更多CO,且电解液占比升高。研究结果可为锂离子电池空运安全性研究提供理论依据。     

Lithium ion battery energy storage systems (BESS) hazards

There has been an increase in the development and deployment of battery energy storage systems (BESS) in recent years. In particular, BESS using lithium-ion batteries have been prevalent, which is mainly due to their power density, performance, and economical aspects. BESS have been increasingly used in residential, commercial, industrial, and utility applications for peak shaving or grid support. As the number of installed systems is increasing, the industry has also been observing more field failures that resulted in fires and explosions. Lithium-ion batteries contain flammable electrolytes, which can create unique hazards when the battery cell becomes compromised and enters thermal runaway. The initiating event is frequently a short circuit which may be a result of overcharging, overheating, or mechanical abuse. During the exothermic reaction process (i.e., thermal runaway), large amounts of flammable and potentially toxic battery gas will be generated. The released gas largely contains hydrogen, which is highly flammable under a wide range of conditions. This may create an explosive atmosphere in the battery room or storage container. As a result, a number of the recent incidents resulted in significant consequences highlighting the difficulties on how to safely deal with the hazard. This paper identifies fire and explosion hazards that exist in commercial/industrial BESS applications and presents mitigation measures. Common threats, barriers, and consequences are conceptually shown and how they would be identified in a hazard mitigation analysis (HMA). Mitigation measures that can be implemented to reduce the risk of a fire or an explosion are discussed. The presented information is intended to provide practical information to professionals and authorities in this fairly new industry to assure that prevention and mitigation strategies can be effectively implemented and that the regulatory requirement of the HMA can be met.     

相变材料填充率影响锂电池组热失控传播特性的实验研究

复合相变材料(PCM)应用于锂电池组的热管理是当前研究的热点。然而,PCM对锂电池组热失控传播特性的影响规律仍不甚明晰。实验研究了不同PCM填充率对锂电池组的影响,分析其热失控触发时间、最高温度、质量损失和热释放速率等参数变化规律。结果发现,添加PCM后,电池表面温度、CO和SO₂浓度均出现了不同程度的降低,但对热释放速率没有明显的影响。PCM填充率为0%和10%的电池组均发生了热失控传播,而30%、50%、100%的PCM填充率能有效阻隔热失控传播的发生。     

锂离子电池热解气体爆炸极限测定及其危险性分析

为定量研究锂离子电池热失控的危险性,利用锂离子电池在滥用条件下释放气体的种类及体积分数,计算锂离子电池热解气体爆炸极限并研究锂电池荷电状态对热解气体爆炸极限的影响。结果表明:在一定热失控条件下锂离子电池荷电状态为100%时其热解气爆炸下限为6.22%,上限为38.4%,在相同热失控条件下,锂离子电池热解气体的爆炸极限范围随着荷电状态的升高而增大,锂电池的荷电状态对热解气体的爆炸上限影响较大而对爆炸下限影响较小。在相似条件下,锂离子电池热解气体的爆炸极限范围比普通烃类气体大,一旦锂电池发生热失控会对锂离子电池运输造成潜在威胁。     

阻燃电解液改善钛酸锂电池体系热稳定性研究

为了提高锂离子电池安全性,将碳酸亚乙烯酯、亚硫酸丙烯酯与二甲基乙酰胺加入到1.0mol/L LiPF_6/碳酸乙烯酯+碳酸二乙酯(1∶1wt%)的基准电解液中,配制成阻燃电解液。运用C80微量量热仪对钛酸锂负极(放电至1.0V)与基准电解液共存体系、钛酸锂负极(放电至1.0V)与阻燃电解液共存体系进行热稳定性测试,并计算得到热力学参数。对Li/基准电解液/Li_4Ti_5O_(12)和Li/阻燃电解液/Li_4Ti_5O_(12)半电池进行充放电循环测试、循环伏安测试与SEM扫描电镜测试。实验结果表明,钛酸锂负极与阻燃电解液体系反应放出的热量较钛酸锂负极与基准电解液体系减少了35.4%,且具有更高的活化能,提高了钛酸锂电池体系的热稳定性;同时电化学测试结果表明,阻燃电解液与钛酸锂负极有良好的相容性,可以应用到钛酸锂电池体系。     

Internal short circuit and accelerated rate calorimetry tests of lithium-ion cells: Considerations for methane-air intrinsic safety and explosion proof/flameproof protection methods

Researchers with the National Institute for Occupational Safety and Health (NIOSH) studied the potential for lithium-ion cell thermal runaway from an internal short circuit in equipment for use in underground coal mines. In this third phase of the study, researchers compared plastic wedge crush-induced internal short circuit tests of selected lithium-ion cells within methane (CH₄)-air mixtures with accelerated rate calorimetry tests of similar cells. Plastic wedge crush test results with metal oxide lithium-ion cells extracted from intrinsically safe evaluated equipment were mixed, with one cell model igniting the chamber atmosphere while another cell model did not. The two cells models exhibited different internal short circuit behaviors. A lithium iron phosphate (LiFePO₄) cell model was tolerant to crush-induced internal short circuits within CH₄-air, tested under manufacturer recommended charging conditions. Accelerating rate calorimetry tests with similar cells within a nitrogen purged 353-mL chamber produced ignitions that exceeded explosion proof and flameproof enclosure minimum internal pressure design criteria. Ignition pressures within a 20-L chamber with 6.5% CH₄-air were relatively low, with much larger head space volume and less adiabatic test conditions. The literature indicates that sizeable lithium thionyl chloride (LiSOCl₂) primary (non rechargeable) cell ignitions can be especially violent and toxic. Because ignition of an explosive atmosphere is expected within explosion proof or flameproof enclosures, there is a need to consider the potential for an internal explosive atmosphere ignition in combination with a lithium or lithium-ion battery thermal runaway process, and the resulting effects on the enclosure.     

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。     

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。