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In order to clarify inerting effect of liquid nitrogen on the thermal runaway explosion of a 280Ah energy storage lithium battery,based on experiment analysis of composition and explosion limit of battery thermal runaway gas,FLACS was used to simulate explosion overpressure of battery thermal runaway gas in a storage container. Standard experiments and real experiments were carried out to analyze inerting effect of liquid nitrogen on battery thermal runaway gas. Results show that thermal runaway gas explosion overpressure increases gradually with an increase of its volume. Ignition of more than 1.1 m3 of thermal runaway gas can cause serious consequences. A single 280 Ah lithium iron phosphate battery in 100% charged state,heating in a vacuum state,heating in a vacuum state can trigger thermal runaway of the battery and produce 134.6 L of thermal runaway gas with CO2,H2,CO,CH4 and C2H4 as the main components. Thermal runaway gas is a flammable gas,and explosion limit range is between 8.5% and 45.5%. N2 can effectively inert thermal runaway gas and significantly reduce the explosion limit range of thermal runaway gas. Limiting N2 volume fraction is 84.7%. Spray 69 kg liquid nitrogen into a 35 m3 energy storage container to inert battery thermal runaway gas. When volume fraction of N2 is higher than limiting nitrogen volume fraction,battery thermal runaway gas can be effectively inerted,and effective protection time is 2 200 s.

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为明确液氮对280 Ah储能锂电池热失控燃爆的惰化效果,在试验分析电池热失控气体成分和爆炸极限的基础上,利用火焰加速模拟(FLACS)软件模拟计算储能集装箱内电池热失控气体爆炸超压后果,并开展标准试验和实体试验,分析液氮对电池热失控气体的惰化抑爆效果。结果表明:热失控气体爆炸超压随着自身体积的增多逐渐升高,点燃超过1.1 m3热失控气体会造成较为严重的后果;单个100%充电状态的280 Ah磷酸铁锂电池,真空状态下加热可触发电池热失控,并产生134.6 L以CO2、H2、CO、CH4和C2H4为主要成分的热失控气体。热失控气体为可燃气体,爆炸极限范围为8.5%~45.5%;N2能够有效惰化热失控气体,并显著减小热失控气体爆炸极限范围,极限N2体积分数为84.7%;向35 m3储能集装箱内喷射69 kg液氮惰化电池热失控气体,当箱内N2体积分数高于极限N2体积分数时能够有效惰化电池热失控气体,有效保护时间为2 200 s。

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张少禹 (1964—),男,天津人,硕士,研究员,主要从事锂离子电池火灾防控、固定灭火系统、消防产品检测及标准化等方面的研究。E-mail:

王玥,助理研究员。

董海斌,研究员。

陈晔,副研究员。

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张少禹 (1964—),男,天津人,硕士,研究员,主要从事锂离子电池火灾防控、固定灭火系统、消防产品检测及标准化等方面的研究。E-mail:

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张少禹 (1964—),男,天津人,硕士,研究员,主要从事锂离子电池火灾防控、固定灭火系统、消防产品检测及标准化等方面的研究。E-mail:

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董海斌,研究员。

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陈晔,副研究员。

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锂电池热失控爆炸超压及液氮惰化效果分析
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张少禹 , 王玥 , 董海斌 , 陈晔
中国安全科学学报 | 安全工程技术 2024,34(3): 39-44
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中国安全科学学报 | 安全工程技术 2024, 34(3): 39-44
锂电池热失控爆炸超压及液氮惰化效果分析
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张少禹 , 王玥, 董海斌, 陈晔
作者信息
  • 应急管理部 天津消防研究所,天津 300381
  • 张少禹 (1964—),男,天津人,硕士,研究员,主要从事锂离子电池火灾防控、固定灭火系统、消防产品检测及标准化等方面的研究。E-mail:

    王玥,助理研究员。

    董海斌,研究员。

    陈晔,副研究员。

Analysis of thermal runaway explosion overpressure and liquid nitrogen inerting effect of lithium battery
Shaoyu ZHANG , Yue WANG, Haibin DONG, Ye CHEN
Affiliations
  • Tianjin Fire Science and Technology Research Institute of MEM,Tianjin,300381,China
出版时间: 2024-03-28 doi: 10.16265/j.cnki.issn1003-3033.2024.03.0878
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为明确液氮对280 Ah储能锂电池热失控燃爆的惰化效果,在试验分析电池热失控气体成分和爆炸极限的基础上,利用火焰加速模拟(FLACS)软件模拟计算储能集装箱内电池热失控气体爆炸超压后果,并开展标准试验和实体试验,分析液氮对电池热失控气体的惰化抑爆效果。结果表明:热失控气体爆炸超压随着自身体积的增多逐渐升高,点燃超过1.1 m3热失控气体会造成较为严重的后果;单个100%充电状态的280 Ah磷酸铁锂电池,真空状态下加热可触发电池热失控,并产生134.6 L以CO2、H2、CO、CH4和C2H4为主要成分的热失控气体。热失控气体为可燃气体,爆炸极限范围为8.5%~45.5%;N2能够有效惰化热失控气体,并显著减小热失控气体爆炸极限范围,极限N2体积分数为84.7%;向35 m3储能集装箱内喷射69 kg液氮惰化电池热失控气体,当箱内N2体积分数高于极限N2体积分数时能够有效惰化电池热失控气体,有效保护时间为2 200 s。

锂电池  /  热失控  /  爆炸超压  /  液氮  /  惰化效果  /  火焰加速模拟(FLACS)

In order to clarify inerting effect of liquid nitrogen on the thermal runaway explosion of a 280Ah energy storage lithium battery,based on experiment analysis of composition and explosion limit of battery thermal runaway gas,FLACS was used to simulate explosion overpressure of battery thermal runaway gas in a storage container. Standard experiments and real experiments were carried out to analyze inerting effect of liquid nitrogen on battery thermal runaway gas. Results show that thermal runaway gas explosion overpressure increases gradually with an increase of its volume. Ignition of more than 1.1 m3 of thermal runaway gas can cause serious consequences. A single 280 Ah lithium iron phosphate battery in 100% charged state,heating in a vacuum state,heating in a vacuum state can trigger thermal runaway of the battery and produce 134.6 L of thermal runaway gas with CO2,H2,CO,CH4 and C2H4 as the main components. Thermal runaway gas is a flammable gas,and explosion limit range is between 8.5% and 45.5%. N2 can effectively inert thermal runaway gas and significantly reduce the explosion limit range of thermal runaway gas. Limiting N2 volume fraction is 84.7%. Spray 69 kg liquid nitrogen into a 35 m3 energy storage container to inert battery thermal runaway gas. When volume fraction of N2 is higher than limiting nitrogen volume fraction,battery thermal runaway gas can be effectively inerted,and effective protection time is 2 200 s.

lithium battery  /  thermal runaway  /  explosion overpressure  /  liquid nitrogen  /  inerting effect  /  flame accelaratition simulatation (FLACS)
张少禹, 王玥, 董海斌, 陈晔. 锂电池热失控爆炸超压及液氮惰化效果分析. 中国安全科学学报, 2024 , 34 (3) : 39 -44 . DOI: 10.16265/j.cnki.issn1003-3033.2024.03.0878
Shaoyu ZHANG, Yue WANG, Haibin DONG, Ye CHEN. Analysis of thermal runaway explosion overpressure and liquid nitrogen inerting effect of lithium battery[J]. China Safety Science Journal, 2024 , 34 (3) : 39 -44 . DOI: 10.16265/j.cnki.issn1003-3033.2024.03.0878
在“双碳”目标背景下,锂离子电池因其具有高能量密度和长寿命等特点,在电动车、便携式电子产品和电化学储能等各个领域被广泛被用作化石燃料的替代品[1-3]。在大规模应用过程中,其生命周期内因热失控引起的火灾和爆炸事故给人民生命和财产安全造成巨大威胁[4-5]
国内外学者对锂电池热失控爆炸后果及火灾灭火剂开展了大量试验研究。SOMANDEPALI[6]研究发现,100%充电状态的锂碳氧化物电池在热失控气体爆炸时的爆炸超压可高达0.7MPa。WANG Huaibin等[7]提出,磷酸铁锂电池热失控气体爆炸下限更低更容易被点燃,且最大爆炸超压更高。针对锂离子电池热失控火灾使用的灭火剂主要有C6F12O、C3HF7、CO2和N2,试验测试得到对应的灭火最低体积分数分别为7%、9%、25%~30%、40%[6]。WANG Qingsong等[8]使用C6F12O、C3HF7迅速扑灭了钛酸锂单体电池、盒装电池和小型电池组火灾,但电池内部剧烈化学反应仍在不断进行,热失控可燃气体不断从电池中喷出,电池存在复燃的情况。XU Jiajia等[9]发现,向三元锂离子电池施加CO2、C3HF7等灭火剂后可有效扑救电池热失控火灾,但同样存在复燃现象。庄卫强等[10]在动力锂离子电池热失控后长时间供给CO2和N2,对气体爆炸有较好的抑制效果,且CO2的灭火抑爆性优于N2。为解决CO2、C3HF7、N2等灭火剂无法在短时间内将热失控电池的表面温度降低到安全水平的问题,HUANG Zonghou等[11]开展试验,发现液氮能够有效降低电池表面温度,延缓电池内部热失控发生。
综上,液氮除具有灭火抑爆作用外,还具有降温延缓热失控发生的作用,但目前尚缺乏液氮对大容量锂离子电池热失控燃爆惰化效果的分析研究。因此,笔者拟在分析280 Ah储能锂离子电池热失控气体成分和爆炸极限范围的基础上,使用火焰加速模拟(Flame Accelaratition Simulatation,FLACS)软件模拟储能集装箱内热失控气体爆炸超压后果,并开展标准试验和储能集装箱实体试验,分析评价液氮扑救电池热失控的惰化效果,以期为液氮灭火惰化抑爆的应用提供一定的技术支撑。
磷酸铁锂电池在受热、过充、外短路等条件下,内部隔膜破损会导致热失控的发生。热失控过程中,电池会发生固体电解质界面分解、负极活性物质与电解质反应、正极活性物质与电解质之间反应、电解液分解以及负极活性物质与粘合剂之间反应等[12-13],这些反应不以准确的给定顺序发生,部分反应会同时发生。根据电池表面温度变化情况可将热失控会分成3个阶段[14],每个阶段均会发生电池部分永久性损伤。由于剧烈的链式反应引发电池内部热失控,伴随产生大量的H2、CH4、C2H4、CO和CO2等混合气体[15-16]。混合气体从排气阀迅速喷出,热失控排气气流可能达到超音速和湍流状态[17-18]
图1为320L锂离子电池热失控气体测试试验装置。装置内部有效体积为320L,设置温度、压力等多路传感器用于采集电池热失控过程中电池表面温度和电池周围环境压力的变化情况。收集的热失控气体可用于测试气体成分、爆炸极限等燃爆参数。试验过程中使用的样品为280 Ah磷酸铁锂电池,电池尺寸为174mm(长)×72mm(宽)×208mm(高)。电池正极材料为磷酸铁锂,负极材料为石墨(C)。试验开始前,使用双向可编程直流电源以34.67 A恒流条件下充电至3.65 V,之后,转恒压充电至5.2 A,最终,达到100%充电状态。试验过程中,将加热片与电池最大表面积一侧靠近后,使用耐高温铝箔胶带固定,设置加热片升温速度为4~7℃/min。为降低空气对热失控可燃气体爆炸极限和气体成分测试影响,同时,降低电池热失控后爆炸危险性,在试验开始前将试验装置内抽真空至1.3 kPa。
图2为磷酸铁锂电池热失控过程中温度和压力变化情况。电池热失控释放可燃气体后装置内绝对压力达到43.8 kPa。根据理想气体状态方程,计算得到,在常温常压(0.1 MPa,25℃)状态下,试验过程中单块280 Ah电池热失控后产生的气体体积为134.6 L。试验过程中,在第1个阶段,电池表面温度会随着高温热源逐渐升高,周围的压力和温度在小范围内波动变化,此阶段经历约为1 146s,电池表面温度上升至89.74℃。在第2个阶段,电池表面温度继续上升,电池内部电解液不断蒸发并产生热失控气体。电池内部压力逐渐升高,当压力超过安全阀开启压力后,安全阀开启,电池表面温度出现小幅度下降后迅速升高,电池开始向周围释放可燃气体,同时伴随着周围压力的上升。此阶段经历约为 3 616s,电池表面温度最高上升至137.44 ℃。该阶段仅产生少量可燃气体,约为35L。在第3阶段,电池温度达到最大值,电池迅速向周围释放大量可燃气体,可燃气体体积大约为99.17L,平均气体释放速率为9.63L/min,此阶段为电池集中产气阶段,产气体积占总体积的73.68%。通过真空采样泵从装置内采集50L热失控气体,按照《空气中可燃气体爆炸极限测定方法》(GB/T 12474—2008)标准方法,采用5.0 L玻璃容器测试热失控气体在常温常压下的爆炸极限,为8.5%~45.5%。利用气相色谱仪分析磷酸铁锂电池热失控气体成分,分析结果为:CO2、H2、CO、CH4、C2H4等组分体积分数分别为44.8%、41%、6.3%、4.3%、3.8%。
利用FLACS软件按照1:1搭建35m3储能电池集装箱模型,如图3所示。箱体外部尺寸为5 830mm(长)×2 340mm(宽)×2 600mm(高),内部设置4个电池簇,每个电池簇放置8组电池模组。物理模型设置最小网格尺寸为0.1m,最大网格尺寸为0.81m,划分网格数量为540 204个,设置模拟气体组分为44.8%CO2、41%H2、6.3%CO、4.3%CH4、3.8%C2H4。假定电池热失控产生的可燃气体在达到当量体积分数(可燃气体与空气中氧气完全反应时的体积分数)26%时发生燃爆,点火源设定在可燃气体气云中心。储能集装箱内部有效体积为33.85m3,当量体积分数下热失控气体最大体积为8.8m3,从0.286~8.8 m3,间隔设置16个不同体积的热失控气体,模拟计算这16个场景下发生爆炸的最大爆炸超压ΔPmax;内部间隔0.2m设置74个监测点,监测爆炸过程中压力随时间的变化情况。
ΔPmax随热失控可燃气体体积变化情况如图4所示。当气体体积为8.8m3被点燃时,ΔPmax达226 kPa,此超压足以将整个集装箱完全损坏[19];当气体体积为4.4 m3和2.2 m3被点燃时,ΔPmax分别降低为196.4和89.7 kPa,前者ΔPmax的降低较为有限,后者与8.8m3相比ΔPmax下降60.31%。当气体体积为1.1m3被点燃时,ΔPmax降为41.1 kPa,与8.8m3相比,ΔPmax降低81.8%,此时的ΔPmax同样能将普通房屋损坏,并对集装箱内的人员造成较为严重的伤害。
可燃气体爆炸极限范围会受到周围环境中N2等惰性气体体积分数的影响,惰性气体对爆炸下限影响相对较低,但会显著降低爆炸上限。随着惰性气体的增加,爆炸上下限会不断接近,爆炸极限范围随之降低,故惰性气体存在一个极限体积分数,周围环境中惰性气体体积占比超过这个体积分数,可燃气体体积分数无论如何变化均不会被引燃。以N2作为惰性气体,以测试得到的电池热失控气体作为研究对象,依据《可燃气体或蒸气极限氧浓度测定方法》(GB/T 38301—2019)标准试验方法测试得到热失控可燃气体的极限N2体积分数,为电池热失控液氮惰化抑爆措施中液氮喷射速度、喷射量、喷射位置、喷射时间等的设计提供技术支撑。
对于电池热失控气体,当未充入N2时,爆炸上限为45%,当充入20%和40%体积分数的N2时,爆炸上限分别下降至33%和18%。当N2充入体积接近60%时,爆炸上下限重合,N2超过该体积分数后热失控气体不会发生爆炸。通过测试得到极限N2体积分数为84.7%,对应极限氧气体积分数为6.83%,对应N2充入体积分数不低于60%。对于35m3的电池储能集装箱,若施加N2惰化,假设集装箱内均匀分布且相对密封,则需要充入不少于20.31m3 的N2才能够有效惰化阻止热失控气体爆炸。
为明确液氮在实际储能集装箱中惰化效果,搭建实尺寸电池储能集装箱,开展电池热失控和液氮惰化抑爆试验。以1:1尺寸搭建35m3电池储能集装箱,如图5所示。集装箱尺寸为5 830mm(长)× 2 340mm(宽)×2 600mm(高)。试验电池集装箱主要包括电池组、泄压口和N2传感器。试验前,将5块 280 Ah磷酸铁锂电池充电至100%充电状态,将电池紧贴并排摆放,在第2块和第3块电池之间安装电加热片。加热片外形尺寸180mm(长)×140mm(宽)×2mm(厚),额定功率800 W,交流电压为 220 V。加热电池至热失控,电池热失控后释放大量可燃气体,电池释放可燃气体结束后喷放液氮进行惰化抑爆。液氮喷射专用喷头的流量系数k为23.3,距离模组上边缘0.8m,喷口压力0.30 MPa,液氮喷射时间为120s,喷入液氮总质量为69kg。在储能集装箱的左侧、中间和右侧的顶部设置3支高精度N2传感器,在右侧底部设置1支高精度N2传感器,如图5b所示。
试验过程中,N2体积分数随时间的变化情况如图6所示。向储能集装箱喷射69kg液氮后,底部的N2传感器体积分数经过252s达到最大值96.85%,顶部N2传感器在经过440s达到最大值96.68%。由于试验集装箱处于正压状态,且集装箱不是完全密封,随着液氮喷入后不断气化,试验集装箱内压力逐渐升高,气化后的N2向外部溢出速度逐渐加快,集装箱内N2体积分数的逐渐下降,N2体积分数高于极限N2体积分数84.53%的时间为2 200s。在2 200s时间内,采用2.0 J电火花点火,间隔30s点火一次,均未出现燃爆现象。
1) 100%充电状态下,280 Ah磷酸铁锂电池在真空状态下热失控共产生134.6L可燃气体,电池
热失控产气集中于第3阶段,产气比例超过73.68%,平均产气速率为9.63 L/min。对应爆炸极限范围为8.5%~45.5%,可燃气体成分以CO2、H2、CO、CH4和C2H4为主。
2) FLACS对不同体积可燃气体在储能集装箱内爆炸超压的模拟结果表明:随着电池热失控气体体积的增加爆炸压力随之升高。当热失控气体体积为1.1 m3被点燃时,最大爆炸超压降低为41.1 kPa,便会造成较为严重的危害。
3) N2体积分数的增加,会显著降低热失控气体的爆炸上限,并缩短爆炸极限范围。当N2体积分数达到极限N2体积分数84.7%时,爆炸上限和爆炸下限重合。N2体积分数超过极限N2体积分数后,可燃气体均不会被引燃。
4) 在120s时间内向35m3储能集装箱内喷射69kg液氮,当箱内N2体积分数高于极限N2体积分数时,能够有效惰化电池热失控气体,且有效保护时间为2 200s。
  • “十四五”国家重点研发计划课题(2021YFB2402003)
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doi: 10.16265/j.cnki.issn1003-3033.2024.03.0878
  • 接收时间:2023-09-20
  • 首发时间:2025-07-09
  • 出版时间:2024-03-28
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  • 收稿日期:2023-09-20
  • 修回日期:2023-12-28
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“十四五”国家重点研发计划课题(2021YFB2402003)
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    应急管理部 天津消防研究所,天津 300381
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