Experimental study on the thermal runaway and its propagation of a lithium-ion traction battery with NCM cathode under thermal abuse
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摘要: 以电动汽车车用额定容量为42 A·h的三元方壳锂离子电池单体和模组为研究对象，研究其在加热条件下单体的绝热热失控特性及成组后侧向加热热失控蔓延特性。结果表明，锂离子电池在发生热失控时，内部最高温度可达920 ℃，电池表面和内部最大温差达403 ℃；热失控首先在迎向热流的面触发，随后蔓延至整个电池；满电状态下的锂离子电池内部热失控蔓延时间介于8～12 s；热失控蔓延过程中锂离子电池的温度特征与绝热热失控测试相比存在较大差异性；热失控喷发颗粒物中，LiF及石墨质量分数占80%以上；模组中失控电池产生的总能量中用于自身加热和喷发损失的占90%左右，热失控释放总能量的10%足以触发热失控蔓延。本文为研究三元锂离子电池模组安全设计、热失控蔓延抑制及新能源汽车的火灾事故调查提供了参考。Abstract: Traction battery is the core component of the electric vehicle. To obtain longer driving ranges, conventional lithium-ion batteries with LiMn2O4, LiCoO2, and LiFePO4 cathodes were gradually replaced by LiNixCoyMn1−x−yO2 batteries. With the increasing energy density and chemical activity of the lithium-ion traction battery, its thermal stability gradually decreases and safety hazards become increasingly serious. In recent years, thermal runaway incidents with traction batteries have occurred frequently at home and abroad, seriously disturbing the development of electric vehicles. Solving the safety problems associated with thermal runaway(TR) and thermal runaway propagation(TRP) of the lithium-ion battery is urgent. In this paper, TR and its propagation behavior, associated with a 42 A·h prismatic lithium-ion battery with a LiNi1/3Co1/3Mn1/3O2 cathode for electric vehicles, were studied under thermal abuse conditions on the cell and module levels. The results indicate that the maximum temperature approaches 920 ℃ inside the cell. The maximum temperature difference is up to 403 ℃ within the cell during TR, and the maximum temperature rise rate inside the cell is 40 ℃·s−1. The TRP time within a lithium-ion battery is 8–12 s under 100% state-of-charge (SOC), and the duration of the vent is 14–18 s. The temperature characteristics of the lithium-ion battery display large differences for the TRP test and adiabaticTR test. In a propagation test, the TR initiates from a forward surface toward the failure point, whereas under the adiabatic test the TR occurs simultaneously in the cell. More than 80% of the particles vented from the cell are LiF and graphite during the adiabatic test. Approximately 90% of the heat released by the TR is used for heating the residual and venting particles of the cell. The study offers a reference guide for the safety design and mitigation strategy of TRP in lithium-ion battery modules, and accident investigations of new energy vehicles.
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Key words:
- lithium-ion battery /
- thermal runaway /
- thermal runaway propagation /
- energy storage /
- safety
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图 1 内置热电偶方案及其对电池性能的影响。（a）步骤；（b）开路电压测量结果；（c）内阻测量结果
Figure 1. The built-in strategy of thermocouples and its influence on the performance of battery sample: (a) insertion steps; (b) open-circuit-voltage; (c) internal resistance
图 2 使用EV-ARC进行了锂电池的绝热热失控测试
Figure 2. Experimental setup for the adiabatic thermal runaway tests of lithium-ion batteries using EV-ARC
图 3 热失控蔓延实验设计
Figure 3. Experimental setup for the thermal runaway propagation lithium-ion battery module
图 4 电池绝热热失控测试过程中的温度、电压特征图
Figure 4. Voltage, temperature, and temperature rate of lithium-ion battery during the EV-ARC test
图 5 热失控过程不同温度阶段内部反应
Figure 5. Chemical reactions inside the lithium-ion battery at different temperature ranges
图 6 电池热失控过程的内部和表面温度
Figure 6. Internal and surface temperatures of lithium-ion battery during thermal runaway in EV-ARC test
图 7 电池热失控前后材料化学分析。（a）未失控正极扫描电镜照片；（b）失控后正极残骸扫描电镜照片；（c）喷发颗粒物扫描电镜照片；（d）未失控、失控后、喷发颗粒能谱结果；（e） 喷发颗粒物及失控后正极X射线衍射图
Figure 7. Chemical analysis of the lithium-ion battery before and after thermal runaway: (a) SEM of cathode materials before thermal runaway; (b) SEM of residual cathode after thermal runaway; (c) SEM of vent particles; (d) EDS of element analysis on the cathode before and after thermal runaway ;(e) XRD of vent particles and cathode materials after thermal runaway
图 9 热失控蔓延中电池的喷发特征。（1a）1#电池，0 s；（1b）1#电池，154 s；（1c）1#电池，161 s；（1d）1#电池，0 s；（1e）1#电池，154 s；（1f）1#电池，161 s；（2a）2#电池，212 s；(2b) 2#电池，218 s；（3a）3#电池，274 s；（3b）2#电池，280 s；（4a）4#电池，380 s；（4b）4#电池，393 s
Figure 9. Vent characteristics in thermal runaway propagation: （1a）1# Cell，0 s；(1b) 1# Cell，154 s；(1c) 1# Cell，161 s；（1d）1# Cell，0 s；(1e) 1# Cell，154 s；(1f) 1# Cell，161 s；（2a）2# Cell，212 s；(2b) 2# Cell，218 s；（3a）3# Cell，274 s；(3b) 2# Cell，280 s；（4a）4# Cell，380 s；(4b) 4# Cell，393 s
图 10 热失控蔓延过程中温度特征
Figure 10. Temperature characteristics in thermal runaway propagation
图 11 三元锂电池的热失控蔓延特性
Figure 11. Characteristics of thermal runaway propagation for Li(NiCOMn)1/3O2 battery
图 12 热失控响应及质量损失
Figure 12. Thermal runaway response and mass loss in thermal runaway propagation
图 13 热失控蔓延过程中温度、电压的响应
Figure 13. Temperature and voltage responses during thermal runaway propagation test
图 14 绝热热失控与侧向加热热失控过程中电池内部温升速率的对比
Figure 14. Comparison of the temperature rise rate between EV-ARC test and side heating during thermal runaway propagation
图 16 热失控蔓延至不同阶段时相邻电池内放的温度分布情况[36]. （a）i#电池失控达到最高温度; （b）i#电池加热（i+1）#电池; （c）（i+1）#电池达到热失控触发温度TTR-ARC; （d）（i+1）#电池失控达到最高温度
Figure 16. Temperature distribution of adjacent batteries in different stages of thermal runaway propagation: （a）the maximum temperature of i# in TR; （b）i# heats（i+1）#; （c）the temperature of（i+1）#reachs to TTR-ARC; （d）the temperature of（i+1）#reachs to Tmax
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