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: 以電動汽車車用額定容量為42 A·h的三元方殼鋰離子電池單體和模組為研究對象，研究其在加熱條件下單體的絕熱熱失控特性及成組后側向加熱熱失控蔓延特性。結果表明，鋰離子電池在發生熱失控時，內部最高溫度可達920 ℃，電池表面和內部最大溫差達403 ℃；熱失控首先在迎向熱流的面觸發，隨后蔓延至整個電池；滿電狀態下的鋰離子電池內部熱失控蔓延時間介于8～12 s；熱失控蔓延過程中鋰離子電池的溫度特征與絕熱熱失控測試相比存在較大差異性；熱失控噴發顆粒物中，LiF及石墨質量分數占80%以上；模組中失控電池產生的總能量中用于自身加熱和噴發損失的占90%左右，熱失控釋放總能量的10%足以觸發熱失控蔓延。本文為研究三元鋰離子電池模組安全設計、熱失控蔓延抑制及新能源汽車的火災事故調查提供了參考。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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圖 1 內置熱電偶方案及其對電池性能的影響。（a）步驟；（b）開路電壓測量結果；（c）內阻測量結果
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
圖 2 使用EV-ARC進行了鋰電池的絕熱熱失控測試
Figure 2. Experimental setup for the adiabatic thermal runaway tests of lithium-ion batteries using EV-ARC
圖 3 熱失控蔓延實驗設計
Figure 3. Experimental setup for the thermal runaway propagation lithium-ion battery module
圖 4 電池絕熱熱失控測試過程中的溫度、電壓特征圖
Figure 4. Voltage, temperature, and temperature rate of lithium-ion battery during the EV-ARC test
圖 5 熱失控過程不同溫度階段內部反應
Figure 5. Chemical reactions inside the lithium-ion battery at different temperature ranges
圖 6 電池熱失控過程的內部和表面溫度
Figure 6. Internal and surface temperatures of lithium-ion battery during thermal runaway in EV-ARC test
圖 7 電池熱失控前后材料化學分析。（a）未失控正極掃描電鏡照片；（b）失控后正極殘骸掃描電鏡照片；（c）噴發顆粒物掃描電鏡照片；（d）未失控、失控后、噴發顆粒能譜結果；（e） 噴發顆粒物及失控后正極X射線衍射圖
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
圖 9 熱失控蔓延中電池的噴發特征。（1a）1#電池，0 s；（1b）1#電池，154 s；（1c）1#電池，161 s；（1d）1#電池，0 s；（1e）1#電池，154 s；（1f）1#電池，161 s；（2a）2#電池，212 s；(2b) 2#電池，218 s；（3a）3#電池，274 s；（3b）2#電池，280 s；（4a）4#電池，380 s；（4b）4#電池，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
圖 10 熱失控蔓延過程中溫度特征
Figure 10. Temperature characteristics in thermal runaway propagation
圖 11 三元鋰電池的熱失控蔓延特性
Figure 11. Characteristics of thermal runaway propagation for Li(NiCOMn)1/3O2 battery
圖 12 熱失控響應及質量損失
Figure 12. Thermal runaway response and mass loss in thermal runaway propagation
圖 13 熱失控蔓延過程中溫度、電壓的響應
Figure 13. Temperature and voltage responses during thermal runaway propagation test
圖 14 絕熱熱失控與側向加熱熱失控過程中電池內部溫升速率的對比
Figure 14. Comparison of the temperature rise rate between EV-ARC test and side heating during thermal runaway propagation
圖 16 熱失控蔓延至不同階段時相鄰電池內放的溫度分布情況[36]. （a）i#電池失控達到最高溫度; （b）i#電池加熱（i+1）#電池; （c）（i+1）#電池達到熱失控觸發溫度TTR-ARC; （d）（i+1）#電池失控達到最高溫度
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
圖 17 熱失控蔓延過程中相鄰電池能流分布
Figure 17. Energy flow distribution of adjacent batteries during thermal runaway propagation
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