Article(id=1149743084583432546, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1149743083069288795, articleNumber=1003-3033(2024)06-0065-08, orderNo=null, doi=10.16265/j.cnki.issn1003-3033.2024.06.0945, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1702483200000, receivedDateStr=2023-12-14, revisedDate=1710518400000, revisedDateStr=2024-03-16, acceptedDate=null, acceptedDateStr=null, onlineDate=1752049712558, onlineDateStr=2025-07-09, pubDate=1719504000000, pubDateStr=2024-06-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752049712558, onlineIssueDateStr=2025-07-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752049712558, creator=13701087609, updateTime=1752049712558, updator=13701087609, issue=Issue{id=1149743083069288795, tenantId=1146029695717560320, journalId=1146031787341344770, year='2024', volume='34', issue='6', pageStart='1', pageEnd='252', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752049712197, creator=13701087609, updateTime=1756468919644, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1168278582599098697, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1149743083069288795, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1168278582599098698, tenantId=1146029695717560320, journalId=1146031787341344770, issueId=1149743083069288795, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=65, endPage=72, ext={EN=ArticleExt(id=1149743084826702179, articleId=1149743084583432546, tenantId=1146029695717560320, journalId=1146031787341344770, language=EN, title=Simulation study on heat transfer of thermal runaway lithium-ion battery in confined space, columnId=1149733269173878863, journalTitle=China Safety Science Journal, columnName=Safety engineering technology, runingTitle=null, highlight=null, articleAbstract=

To investigate the source and proportion of thermal runaway heat transfer of lithium-ion batteries in confined conditions space such as aviation transportation,the 18650 lithium-ion battery (100% state of charge) with lithium cobalt oxide (LCO) as the cathode material was used. The heat transfer model of thermal runaway of lithium-ion batteries was proposed by ANSYS Fluent software. Furthermore,the pyrolysis gas generated by the first battery and its thermal runaway was used as the heat source,and the second battery was heated to thermal runaway through radiation and convection. The results showed that when 2nd battery reached the thermal runaway temperature,the heat generated by the internal side reaction accounted for 30.01% of the total energy. The gas combustion generated by the 1st battery thermal runaway provided energy for 2nd battery thermal runaway,accounting for 5.64% of the total energy. When 2nd battery reached the maximum temperature,the heat generated inside the battery accounted for 87.39%,and the energy provided by the gas combustion was 1.76%. the pyrolysis gas combustion accelerates 2nd battery's thermal runaway,though it is a heat source,it is not a heat source. Although the combustion of pyrolysis gas accelerated the thermal runaway process of 2nd battery,the proportion of energy provided was relatively small.

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为探究锂离子电池在航空运输等受限空间条件下的热失控热传递来源及占比,以正极材料钴酸锂(LCO)的18650型锂离子电池(100% 荷电状态)为研究对象。通过ANSYS Fluent软件建立锂离子电池热失控热传递模型,将第1节电池及其热失控产生的热解气体作为热源,通过辐射传热和对流换热对第2节电池进行加热至热失控。研究结果表明:第2节电池达到热失控温度时,电池内部副反应产热占总能量的30.01%;第1节电池热失控产生的气体燃烧为第2节电池热失控提供能量,且占总能量的5.64%;第2节电池达到最高温度时,电池内部产热占比87.39%,气体燃烧提供的能量占比为1.76%;热解气体的燃烧虽然加速第2节电池的热失控进程,但提供的能量所占比例较小。

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张青松 (1977—),男,河北晋州人,博士,教授,主要从事民航危险品运输安全与锂电池火灾方面的研究。E-mail:

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张青松 (1977—),男,河北晋州人,博士,教授,主要从事民航危险品运输安全与锂电池火灾方面的研究。E-mail:

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figureFileSmall=OYKAiDrHQYNPCXlnk/tkuw==, figureFileBig=Ks0ulrX25P93ACGLoJ1dew==, tableContent=null), ArticleFig(id=1168181618700198583, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=CN, label=图5, caption=第2节电池热失控的能量占比, figureFileSmall=OYKAiDrHQYNPCXlnk/tkuw==, figureFileBig=Ks0ulrX25P93ACGLoJ1dew==, tableContent=null), ArticleFig(id=1168181618750530232, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=EN, label=Table 1, caption=

Parameter properties of internal heat generation model of lithium-ion battery

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副反应化学参数 SEI膜分解 负极与电解液反应 正极材料热分解 粘结剂分解 电解液分解
Hi/(J·kg-1) 2.57×105 1.71×106 3.14×105 1.50×106 1.55×105
Wi/ (kg·m-3) 6.10×102 6.10×102 1.20×103 8.14×104 4.07×102
Ai/s-1 1.67×1015 2.50×1013 6.67×1013 1.92×1025 5.14×1025
Ea,i / (J·mol-1) 1.35×105 1.35×105 1.40×105 2.86×105 2.74×105
), ArticleFig(id=1168181618809250489, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=CN, label=表1, caption=

锂离子电池内部产热模型参数取值

, figureFileSmall=null, figureFileBig=null, tableContent=
副反应化学参数 SEI膜分解 负极与电解液反应 正极材料热分解 粘结剂分解 电解液分解
Hi/(J·kg-1) 2.57×105 1.71×106 3.14×105 1.50×106 1.55×105
Wi/ (kg·m-3) 6.10×102 6.10×102 1.20×103 8.14×104 4.07×102
Ai/s-1 1.67×1015 2.50×1013 6.67×1013 1.92×1025 5.14×1025
Ea,i / (J·mol-1) 1.35×105 1.35×105 1.40×105 2.86×105 2.74×105
), ArticleFig(id=1168181618897330874, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=EN, label=Table 2, caption=

Initial values of internal heat generation model of lithium-ion battery

, figureFileSmall=null, figureFileBig=null, tableContent=
参数 初始值 参数 初始值
cs 0.15 ms 1
cn 0.75 mn 1
α 0.04 mp 1
cv 1 mv 1
ce 1 me 1
), ArticleFig(id=1168181618951856827, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=CN, label=表2, caption=

锂离子电池内部产热模型初始值取值

, figureFileSmall=null, figureFileBig=null, tableContent=
参数 初始值 参数 初始值
cs 0.15 ms 1
cn 0.75 mn 1
α 0.04 mp 1
cv 1 mv 1
ce 1 me 1
), ArticleFig(id=1168181619018965692, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=EN, label=Table 3, caption=

Comparison between simulations and experimental data

, figureFileSmall=null, figureFileBig=null, tableContent=
2节电池热失控过程
温度情况
试验数据 仿真结果 误差/%
第1节电池
温度/K
热失控温度 481.55 508.95 5.69
最高温度 1 002.95 946.74 5.6
环境温度最高值/K 545.1 537.03 1.48
第2节电池
温度/K
热失控温度 443.55 473.77 6.81
最高温度 930.45 866.3 6.89
), ArticleFig(id=1168181619102851773, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=CN, label=表3, caption=

仿真数据与试验数据对比

, figureFileSmall=null, figureFileBig=null, tableContent=
2节电池热失控过程
温度情况
试验数据 仿真结果 误差/%
第1节电池
温度/K
热失控温度 481.55 508.95 5.69
最高温度 1 002.95 946.74 5.6
环境温度最高值/K 545.1 537.03 1.48
第2节电池
温度/K
热失控温度 443.55 473.77 6.81
最高温度 930.45 866.3 6.89
), ArticleFig(id=1168181619232875198, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=EN, label=Table 4, caption=

Heat transfer energy analysis in 2ndbattery thermal runawayJ

, figureFileSmall=null, figureFileBig=null, tableContent=
能量来源 发生热
失控时
能量
达到热失
控最高温
度时能量
总能量 电池内部副反应产热 2 529.39 23 634.41
第2节电池热失控过程接受外界能量(热辐射+热对流) 第1节电池热辐射
传递能量
7 733.61 5 618.58
环境对流换热(气体燃烧+散热) 气体燃
烧提供
能量
475.81 475.81
散热 -2 309.61 -2 684.55
), ArticleFig(id=1168181619291595455, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1149743084583432546, language=CN, label=表4, caption=

第2节电池热失控热传递能量分析

, figureFileSmall=null, figureFileBig=null, tableContent=
能量来源 发生热
失控时
能量
达到热失
控最高温
度时能量
总能量 电池内部副反应产热 2 529.39 23 634.41
第2节电池热失控过程接受外界能量(热辐射+热对流) 第1节电池热辐射
传递能量
7 733.61 5 618.58
环境对流换热(气体燃烧+散热) 气体燃
烧提供
能量
475.81 475.81
散热 -2 309.61 -2 684.55
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受限空间锂离子电池热失控热传递仿真研究
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张青松 1 , 贾燕 1 , 翟祺悦 2 , 刘添添 1
中国安全科学学报 | 安全工程技术 2024,34(6): 65-72
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中国安全科学学报 | 安全工程技术 2024, 34(6): 65-72
受限空间锂离子电池热失控热传递仿真研究
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张青松1 , 贾燕1, 翟祺悦2, 刘添添1
作者信息
  • 1 中国民航大学 民航热灾害防控与应急重点实验室,天津 300300
  • 2 北京中航建研航空设计咨询有限公司,北京 100084
  • 张青松 (1977—),男,河北晋州人,博士,教授,主要从事民航危险品运输安全与锂电池火灾方面的研究。E-mail:

Simulation study on heat transfer of thermal runaway lithium-ion battery in confined space
Qingsong ZHANG1 , Yan JIA1, Qiyue ZHAI2, Tiantian LIU1
Affiliations
  • 1 Key Laboratory of Civil Aviation Thermal Hazards Prevention and Emergency Response,Civil Aviation University of China,Tianjin 300300,China
  • 2 Beijing AVIC Jianyan Aviation Design & Consulting Co.,Beijing 100084,China
出版时间: 2024-06-28 doi: 10.16265/j.cnki.issn1003-3033.2024.06.0945
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为探究锂离子电池在航空运输等受限空间条件下的热失控热传递来源及占比,以正极材料钴酸锂(LCO)的18650型锂离子电池(100% 荷电状态)为研究对象。通过ANSYS Fluent软件建立锂离子电池热失控热传递模型,将第1节电池及其热失控产生的热解气体作为热源,通过辐射传热和对流换热对第2节电池进行加热至热失控。研究结果表明:第2节电池达到热失控温度时,电池内部副反应产热占总能量的30.01%;第1节电池热失控产生的气体燃烧为第2节电池热失控提供能量,且占总能量的5.64%;第2节电池达到最高温度时,电池内部产热占比87.39%,气体燃烧提供的能量占比为1.76%;热解气体的燃烧虽然加速第2节电池的热失控进程,但提供的能量所占比例较小。

受限空间  /  锂离子电池  /  热失控热传递  /  Fluent  /  内部副反应  /  气体燃烧

To investigate the source and proportion of thermal runaway heat transfer of lithium-ion batteries in confined conditions space such as aviation transportation,the 18650 lithium-ion battery (100% state of charge) with lithium cobalt oxide (LCO) as the cathode material was used. The heat transfer model of thermal runaway of lithium-ion batteries was proposed by ANSYS Fluent software. Furthermore,the pyrolysis gas generated by the first battery and its thermal runaway was used as the heat source,and the second battery was heated to thermal runaway through radiation and convection. The results showed that when 2nd battery reached the thermal runaway temperature,the heat generated by the internal side reaction accounted for 30.01% of the total energy. The gas combustion generated by the 1st battery thermal runaway provided energy for 2nd battery thermal runaway,accounting for 5.64% of the total energy. When 2nd battery reached the maximum temperature,the heat generated inside the battery accounted for 87.39%,and the energy provided by the gas combustion was 1.76%. the pyrolysis gas combustion accelerates 2nd battery's thermal runaway,though it is a heat source,it is not a heat source. Although the combustion of pyrolysis gas accelerated the thermal runaway process of 2nd battery,the proportion of energy provided was relatively small.

confined space  /  lithium-ion battery  /  thermal runaway heat transfer  /  Fluent  /  internal side reactions  /  gas combustion
张青松, 贾燕, 翟祺悦, 刘添添. 受限空间锂离子电池热失控热传递仿真研究. 中国安全科学学报, 2024 , 34 (6) : 65 -72 . DOI: 10.16265/j.cnki.issn1003-3033.2024.06.0945
Qingsong ZHANG, Yan JIA, Qiyue ZHAI, Tiantian LIU. Simulation study on heat transfer of thermal runaway lithium-ion battery in confined space[J]. China Safety Science Journal, 2024 , 34 (6) : 65 -72 . DOI: 10.16265/j.cnki.issn1003-3033.2024.06.0945
锂离子电池因其能量密度高和使用寿命长的特点,被广泛应用于各个行业,在日常生活中所占的比例越来越重,但其特性带来的安全问题不可忽视[1]。在锂电池热失控过程中,电池内部会进行大量且复杂的化学反应,释放大量热量,加速电池热失控进程,同时,会喷射以气体、气溶胶和固体颗粒形式的电池材料[2],喷射的物质通过燃烧将热量传递到周围环境中,导致环境升温。电池热失控的一个主要危险是将这种能量传递到其他电池中,称作热传递。锂电池热失控会发生连锁反应[3],造成巨大的经济损失。锂离子电池热失控试验耗费大量的时间及金钱,却仍不能准确地测量电池热失控时产生的能量[4]。通过模拟仿真的方式,从机制上分析热失控过程中锂电池自身产热和热解气体燃烧对锂电池热失控传递的影响,考虑到锂离子电池航空运输过程的安全性,对锂离子电池在热失控热传递的研究是非常有意义的。
张青松等[5]通过试验和Fluent仿真的方式研究了锂离子电池热失控的多米诺效应,结果表明:3×3 排列锂电池热失控传播过程展示出3层级的热失控传播方式,各层级间热失控发生时间接近并与下一层级存在一定时间间隔;罗星娜等[6]构建了9个18650型锂离子电池模组的理论模型,并模拟了电池热失控传导过程,分析了在电池热失控传导中产生的多米诺效应,计算了单节电池出现热失控现象对周围电池造成的热危害;齐创等[7]针对锂离子电池是否处于开放环境及是否使用隔热材料,开展了3种不同条件下的电池模组热失控传递试验,结果表明:隔热材料可有效延长电池模组的热传递时间,开放环境延缓热失控的效果较弱,火焰能显著促进电池模组的热传递;王骞等[8]利用COMSOL软件分析了不同排列结构和不同距离电池发生热失控传递的情况,结果表明:插排比顺排对热失控传播速率的降低更有效;随着电池模组热失控的进行,热失控的传播越来越快,电池发生热失控的时间间隔逐渐缩短;在不同方向上增加电池之间的距离会使其他电池发生热失控的时间推后;FENG Xuning等[9]搭建了由6个电池构成的模块,分析模块中第1个电池被穿刺,便触发了热失控传播过程的传热,结果表明:若要引发周围电池热失控,只需提供电池12 %的热失控总能量。火灾可能不会导致热失控的传播,但可能严重破坏电池上方的元件。WALKER等[10]提出一种热失控组分量热仪,该仪器可以区分电池热失控后以各种形式、路径向环境释放的热量,且提供了合理的定量计算方法,该研究成果表明:有20%~30%的热失控能量可以通过电池热失控产物带离电池本体。张青松等[11]基于能量守恒方程和等效替代法,提出一种计算热失控气体燃烧对热失控传播贡献占比的方法,试验结果计算表明:第1节电池热失控气体燃烧释放的能量在第2节电池热失控所需能量中占比达到5.42%,使第2节电池自产热增加42%,热失控时间提前28%。
综上,国内外关于锂离子电池的热失控演化机制方面的研究,主要集中于揭示锂离子电池的热安全隐患,研究方法以试验现象分析为主,对于热失控热传播及其建模方面的研究目前还相对较少。因此,笔者拟以100%荷电状态(State Of Charge,SOC)的18650型锂离子电池为研究对象,通过数值模拟的方式,从机制上深入研究热失控过程,准确计算锂离子电池发生热失控各个阶段产生的能量,并计算受限空间内锂离子电池热失控热传递过程中,第1节电池内部副反应产热及热解气体燃烧产生的热量对第2节电池热失控的影响,以期为锂离子电池热失控传播机制及防控提供理论依据。
以正极材料钴酸锂(Lithium Cobalt Oxide,LCO)的18650型锂离子电池(100% SOC)为研究对象,使用SolidWorks对2节电池及内径300 mm、高度80 mm的圆柱形密闭空间建模,2节电池之间的距离为1mm。电池表面与空气环境存在对流换热,由于模型中2节电池不直接接触,故2节电池之间传热方式为辐射传热。
结合锂离子电池内部副反应产热模型和张青松等[12]提出的的锂离子电池热解气体燃烧产热模型,建立锂离子电池热失控热传递模型。将第1节电池及密闭空间内的气体环境分别作为热源通过辐射传热和对流换热加热第2节电池至热失控。第1节电池及密闭空间内的气体环境热源的设置使用C语言进行编程,将编写的热源代码使用用户自定义函数(User-Defined Function,UDF)功能进行解释及编译,并在仿真过程中分别放入热源。锂离子电池热失控热传递几何模型如图1所示。
在电池发生热失控时,随着温度的不断提高,电池内部会发生固体电解质(Solid Electrolyte Interface,SEI )膜分解、负极材料与电解液反应、正极材料热分解、粘结剂分解和电解质溶液分解等一系列化学反应[13]。根据阿伦尼乌斯公式构建电池热失控时内部发生化学反应产生的热量模型:
  Q = Q s + Q n + Q p + Q v + Q e = H i W i R i
式中: Q为电池热失控内部自产热总能量,J; Q s为SEI膜分解的生热量,J; Q n为负极材料与电解液发生化学反应的生热量,J; Q p为正极材料分解的生热量,J; Q v为粘结剂分解的生热量,J; Q e 为电解液分解的生热量,J;Hi为比热释放量,J/kg; W i 为单位体积碳含量,kg/m3; R i为反应速率,s-1。各副反应产生的热量的计算公式如下:
1) SEI膜分解:
d c s d t 1 = - R s = - A s · e x p - E a s r T · c s m s
式中: c s 为SEI 膜含量;t1为SEI膜反应时间,s;Rs为 SEI膜分解反应速率,s-1; A s为SEI膜分解的
频率因子,s-1; E a s为SEI 膜分解的活化能,J/mol;r为气体常数,r= 8.314 J/(mol·K);T为热力学温度,K;ms为SEI膜分解的反应级数,s-1
2) 负极材料与电解液反应:
d c n d t 2 = - R n = - A n · e x p - E a n r T · c n m n
式中: c n为负极锂离子浓度;t2为负极材料与电解液反应时间,s; R n为负极材料与电解液反应速率,s-1; A n为负极与电解液反应的频率因子,s-1;Ea,n为负极与电解液反应的活化能,J/mol;mn为负极材料与电解液反应的反应级数,s-1
3) 正极材料热分解:
d c p d t 3 = - R p = - A p · α m p · ( 1 - α ) m p · e x p - E a p r T
式中: c p为正极材料浓度;t3为正极材料热分解时间,s; R p为正极材料热分解反应速率,s-1; A p为正极分解的频率因子,s-1;Ea,p为正极分解的活化能,J/mol;α为转换率;mp为正极材料热分解的反应级数,s-1
4) 粘结剂分解:
d c v d t 4 = - R v = - A v · e x p - E a v r T · c v m v
式中: c v为粘结剂浓度;t4为粘结剂分解时间,s;Rv为粘结剂分解反应速率,s-1; A v为粘结剂分解的频率因子,s-1;Ea,v为粘结剂分解的活化能,J/mol;mv为粘结剂分解的反应级数,s-1
5) 电解液分解:
d c e d t 5 = - R e = - A e · e x p - E a s r T · c e m e
式中: c e为电解液浓度;t5为电解液分解时间,s;Re为电解液分解反应速率,s-1; A e为电解液分解的频率因子,s-1;Ea,e为电解液分解的活化能,J/mol;me为电解液分解的反应级数,s-1。通过查阅文献[14-17],各副反应化学参数取值见表1,各副反应参数初始值取值见表2
在单体锂离子电池模型热失控的过程中,导致电池发生热失控的能量由加热装置及自身产热构成。因此,需要设置2部分能量来源,加热装置采用镍铬电热丝半环绕式加热锂离子电池至发生热失控,使用体积热源设置加热装置提供的能量,通过热传导的方式加热锂离子电池。电池自产热热源的设置使用C语言编程不同温度下各副反应的生热量,将编写的热源代码使用UDF功能进行编译,并在仿真过程中放入热源来模拟热失控过程中电池内部的副反应产热。
求解电池内部温度之前,使用SolidWorks软件建模18650型的LCO电池单体,建立模型时将电池简化为直径18mm,高度65mm,各项物性参数取值均匀的圆柱体。然后采用ANSYS workbench进行预处理,使用meshing划分模型网格,再将划分好网格模型导入Fluent中,接着定义模型的初始条件和边界条件,设置合适的步长和迭代次数进行模拟。
加热装置的加热功率为30 W,电池的初始温度为299 K。由于电池处于开放空间,故考虑加热棒与电池之间的热传导及电池表面与空气环境的对流传热。辐射传热在此模型中提供的热量较少,故可忽略其影响。
热量以热传导、热对流及热辐射3种形式传递。对几种传热形式进行建模如下:
1) 内部热传导。热传导是通过直接接触,将热从一个物体传递给另一个物体,或从物体的一部分传递到另一部分的传热方法。为简化计算过程,假设电池为内部性质相同、均匀的圆柱体,电池内部热量传递方程如下:
ρ C p T t = x λ x T x + y λ y T y + z λ z T z + q
式中:ρ为电池密度,kg/m3;Cp为电池的等效比热容,J/(kg·K);t为热传导传热发生时间,s; λ x λ y λ z分别为xyz方向上的导热系数,W/(m2·K);q为电池内部生热热源,W/m3
2) 对流换热。热对流是指热量通过流动介质,由空间的一处传播到另一处的现象。电池模型壁面与空气接触对流换热的边界条件如下:
- λ T d = h T b - T f
式中:λ为电池的等效导热系数,W/(m2·K);d为电池换热表面的外法线;h为对流换热系数,W/(m2·K);Tf为环境温度,K; T b为电池表面温度,K。
3) 辐射换热。辐射是物体通过电磁波传递能量的方式。热辐射是因热的原因而发出辐射能的现象。热辐射在传递能量时不需要互相接触即可进行,是一种非接触传递能量的方式。电池模型壁面与外界辐射传热边界条件设置如下:
- λ T n = ε σ T 1 4 - T 2 4
式中:ε为热辐射系数,W/(m2·K4);σ为玻尔兹曼常量,为5.67×10-8 J/K;T1为辐射面1的温度,K;T2为辐射面2温度,K。
18650型锂离子电池是一个由多个部件构成的内部较为复杂的立体结构。CHEN Sichong等[18]建立了一个锂离子电池内部结构整体模型,模拟了电池温度变化,发现考虑电池内部结构是否分层与仿真得到的结果无显著影响,电池的多层模型不仅会使模型建立变得复杂,还会对仿真的计算速度产生影响。因此,在构建电池模型及定义相关物性参数时,将电池内部视为均匀的圆柱体,物性参数由等效计算所得。简化后锂离子电池的密度可由电池内各物质的平均密度来确定[8]:
ρ = ρ i l i l i
式中:ρi为各种组成物质的密度;li为各种组成材料的厚度。
锂离子电池的等效比热容可由电池组成元素的比热容来确定:
C p = C i l i l i
式中 C i为各种组成物质的比热容,J/(kg·K)。
电池的等效径向导热系数与轴向导热系数的计算公式如下:
λ = λ i l i l i
式中λi为各种组成材料的导热系数,W/(m2·K)。
经过计算及定义电池热力学属性如下:密度ρ=2 962 kg/m3,比热容 C p=970 J/(kg·K),径向导热系数λx=λz=3 W/(m·K),轴向导热系数λy=30 W/(m·K),对流换热系数h=20 W/m2,热辐射系数ε=0.23。
采用ANSYS workbench进行预处理,使用meshing划分模型网格,再将划分好网格模型导入Fluent中,定义模型的初始条件和边界条件,设置合适的步长和迭代次数进行模拟。第1节锂离子电池初始温度设为300 K,第2节锂离子电池初始温度设为296 K,环境初始温度为296 K。仿真过程中实时监测2节电池温度及环境温度,并输出第2节电池热失控过程的表面热流量和总能量,比较仿真结果与张青松等[5]的试验数据,如图2所示。
图2可知:第1节电池开始发生热失控时,电池温度为508.95 K,热失控之后的最高温度为946.74 K,热解气体燃烧造成环境温度升高237.01 K,此时,环境温度达到最高值,为537.03 K,第1节电池开始发生热失控现象247s后,第2节电池也随之达到热失控温度,发生热失控时,电池温度为473.77 K,热失控之后的最高温度为866.3 K,仿真输出的数据与试验数据对比及误差分析见表3。仿真所得的温度数据与试验基本吻合,误差均在10%以内,因此,受限空间内锂离子电池热失控热传递模型是可靠的。
电池内部各副反应开始发生时的温度云图如图3所示。图4通过电池整体温度云图和电池截面温度云图,描述了电池达到热失控最高温度时内部温度的分布情况。
分析第2节锂离子电池热失控的能量来源可知:导致第2节电池发生热失控的能量由内部产生能量和外部接收能量2部分组成,内部产生能量为电池自身副反应产热组成,外部接收的能量由第1节电池对第2节电池的辐射传热以及热解气体燃烧造成环境温度升高与第2节电池之间的对流换热组成。综上,分析第2节电池热失控的能量来源如下:
Q = Q t + Q c + Q r
式中: Q t为内部副反应产热; Q c为对流换热产生能量; Q r为第1节电池热辐射传递能量。其中,对流换热部分中也考虑了锂离子的电池散热情况,当受限空间的环境温度比电池温度低时,电池向环境传递热量。
整理和计算Fluent软件输出的受限空间内第2节电池热失控过程的表面热流量和总能量数据,第2节电池发生热失控时和达到热失控最高温度时其能量来源见表4,第2节电池热失控的能量占比如图5所示。
受限空间内第2节电池发生热失控时的总能量为8 429.21 J,电池内部副反应产热为2 529.39 J,占总能量的30.01%,第2节电池热失控过程接受外界能量为5 899.82 J,占总能量的69.99%,其中,第1节电池热辐射传递能量为7 733.61 J,环境对流换热(气体燃烧+对流散热)为-1 833.8 J。虽然热解气体燃烧通过对流换热的方式为第2节电池提供部分热量,但由于除气体燃烧造成环境升温外,其余时间的环境温度值均低于电池温度,热量由电池向环境传递,故在仿真过程中,电池更多以对流换热的方式进行散热。在对流换热过程中,气体燃烧造成的环境升温为第2节电池热失控提供的能量为475.81 J,占第2节电池热失控总能量的5.64%。张青松等[12]通过试验所得,第1节电池热失控气体燃烧释能共有346.1 J传递到第2节电池,占热失控传播所需能量的5.42%。与文中通过仿真得出的热失控热传递的结论一致。
当第2节电池达到热失控最高温度时,总能量为27 044.25 J,电池内部副反应产热为23 634.41 J,占总能量的87.39%,第2节电池热失控过程接受外界能量为3 409.83 J,占总能量的12.61%,其中,第1节电池热辐射传递能量为5 618.58 J。由于第2节电池发生热失控,电池温度高于第1节电池的温度,此时热量由第2节电池以热辐射的方式向第1节电池传递,故在辐射传热方面,能量在电池达到热失控最高温度时与发生热失控时相比有所降低。环境对流换热(气体燃烧+对流散热)为-2 208.74 J,气体燃烧造成的环境升温为第2节电池热失控提供的能量475.81 J,占第2节电池热失控总能量的1.76%。
通过对比发现,在第2节电池达到热失控温度前,电池接收的外界能量为造成温度升高的主要能量来源,热失控过程中,温度急剧升高,此时电池内部自产热为主要的能量来源。热解气体的燃烧虽然加速第2节电池的热失控进程,但是提供的能量所占比例较小。
1) 第1节电池的温度达到508.95 K时,电池发生热失控,热失控过程中达到的最高温度为946.74 K,热解气体燃烧造成环境温度升高237.01 K,环境温度最高值为537.03 K,第1节电池开始发生热失控现象247s后,第2节电池也随之达到热失控温度,热失控温度为473.77 K,热失控最高温度为866.3 K,仿真结果与试验数据基本吻合,验证了锂离子电池热失控热传递模型的可靠性。
2) 第2节电池达到热失控温度前,电池接收的外界能量为造成温度升高的主要能量来源,热失控过程中,电池温度急剧升高,此时内部自产热为主要的能量来源。热解气体的燃烧虽然加速第2节电池的热失控进程,但是提供的能量所占比例较小。
3) 采用模拟仿真的方式分析受限空间锂离子电池的热失控热传递,从机制上深入研究热失控的过程,计算热失控的各个阶段产生的热量,弥补试验的不足之处。
4) 根据阿伦尼乌斯公式建立锂电池热失控内部产热模型时,各副反应化学参数的取值为查阅文献所选的经验值,忽略了电池的个体差异对仿真结果的影响。后续可继续细化对不同电池内部化学反应的研究,降低个体取值的随机误差,以提高经验值的准确度。
  • 国家自然科学基金资助(U2033204)
  • 中央高校基本科研业务费项目(3122023022)
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2024年第34卷第6期
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doi: 10.16265/j.cnki.issn1003-3033.2024.06.0945
  • 接收时间:2023-12-14
  • 首发时间:2025-07-09
  • 出版时间:2024-06-28
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  • 收稿日期:2023-12-14
  • 修回日期:2024-03-16
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国家自然科学基金资助(U2033204)
中央高校基本科研业务费项目(3122023022)
作者信息
    1 中国民航大学 民航热灾害防控与应急重点实验室,天津 300300
    2 北京中航建研航空设计咨询有限公司,北京 100084
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2种不同金属材料的力学参数

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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