磷酸铁锂电池热失控产物爆炸下限预测方法

袁帅; 台枫; 钱新明; 程东浩

doi:10.11883/bzycj-2023-0452

磷酸铁锂电池热失控产物爆炸下限预测方法

doi: 10.11883/bzycj-2023-0452

袁帅^{1, 2,},
台枫¹,
钱新明²,
程东浩^{1, 3, ,}

1.
中国民航科学技术研究院，北京 101399
2.
北京理工大学爆炸科学与技术国家重点实验室，北京 100081
3.
北京市民航安全分析及预防工程技术研究中心，北京 100028

基金项目: 国家重点研发计划项目（2023YFC3009504）；国家自然科学基金民航联合基金（U2033204）；民航安全能力项目（xxx2146903446）

详细信息

作者简介:
袁　帅（1991－　），男，博士，工程师，yuanshuai@mail.castc.org.cn

通讯作者:
程东浩（1984－　），男，博士，副研究员，chengdh@mail.castc.org.cn

中图分类号: O389; X932
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- 文章访问数: 167
- HTML全文浏览量: 24
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- 被引次数: 0
出版历程
- 收稿日期: 2023-12-19
- 修回日期: 2024-04-19
- 网络出版日期: 2024-04-30

Prediction methods for lower explosion limit of thermal runaway products of lithium iron phosphate batteries

YUAN Shuai^{1, 2
,},
TAI Feng¹,
QIAN Xinming²,
CHENG Donghao^{1, 3
, ,}

1.
China Academy of Civil Aviation Science and Technology, Beijing 101399, China
2.
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China
3.
Engineering and Technical Research Center of Civil Aviation Safety Analysis and Prevention of Beijing, Beijing 100028, China

摘要

摘要: 为准确预测磷酸铁锂电池热失控产物的爆炸下限，在密闭压力容器内开展了磷酸铁锂电池热失控试验，结合热失控特性和气相色谱-质谱联用技术，计算了热失控产物气体组分，基于能量守恒方程和绝热火焰温度，建立磷酸铁锂电池热失控产物爆炸下限的预测模型，并验证了绝热火焰温度法、Le Chatelier法和Jones法的准确性，考察了电解液蒸汽对热失控产物爆炸下限的影响。结果表明，常温下Le Chatelier法计算的爆炸下限偏差最小，为1.14%，绝热火焰温度法偏差最大，为10.02%。在60%~100%荷电状态（state of charge, SOC）范围内，磷酸铁锂电池热失控气体的爆炸下限先升后降。当热失控产物考虑电解液蒸汽时，60% SOC磷酸铁锂电池热失控产物爆炸下限仅为3.93%，较未考虑电解液蒸汽热失控气体的爆炸下限降低了22.49%，这说明电解液蒸汽增加了磷酸铁锂电池热失控产物的爆炸风险。
- 磷酸铁锂电池 /
- 热失控产物 /
- 爆炸下限 /
- Le Chatelier定律 /
- 绝热火焰温度
Abstract: To predict precisely the lower explosion limit of thermal runaway products of lithium iron phosphate batteries, thermal runaway tests of lithium iron phosphate batteries were carried out in a closed pressure vessel. The experiments were carried out at 25 ℃ and 0.1 MPa, and the method was used to analyze the thermal runaway gas production. The vent gas species composition of lithium iron phosphate batteries was analyzed by gas chromatography and mass spectrometry. Combined with the thermal runaway characteristics of the battery and gas chromatography-mass spectrometry (GC-MS) technology, the gas composition of thermal runaway products of lithium iron phosphate batteries was calculated. It was assumed that the thermal runway products released from the relief valve to the first injection were all dimethyl carbonate (DMC), and the secondary injection gas was the mixed gas generated by the internal chemical reaction, which is mainly composed of H₂, CO₂, CO, CH₄, and C₂H₄. A prediction model of the lower explosion limit of thermal runaway products was established based on the energy conservation equation and adiabatic flame temperature. The prediction methods of lower explosion limit of multicomponent gases based on adiabatic flame temperature, Le Chatelier law method, and Jones method were verified, and the influence of electrolyte vapor on the lower explosion limit of thermal runaway production was also investigated. The smallest deviation of the lower explosion limit calculated by the Le Chatelier law method at normal temperature and pressure was 1.14%, and the largest deviation of the lower explosion limit calculated by the adiabatic flame temperature method was 10.02%. Within the range from 60% SOC to 100% SOC, the lower explosion limit of the thermal runaway gases increases first and then decreases. When the electrolyte vapor is considered in the thermal runaway products, the lower explosion limit of thermal runaway products of lithium iron phosphate batteries with 60% SOC is only 3.93%, which is 22.49% lower than that of the thermal runaway gas without considering the electrolyte vapor. Actually, the electrolyte vapor is contained in the thermal runaway products of lithium iron phosphate batteries. These results indicate that the addition of electrolyte vapor increases the explosion risk of thermal runaway production of lithium iron phosphate batteries.
- lithium iron phosphate battery /
- thermal runway product /
- lower explosion limit /
- Le Chatelier’s law /
- adiabatic flame temperature

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图 1 密闭压力容器示意图

Figure 1. Diagram of the closed pressure vessel

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图 2 100% SOC电池的热失控过程

Figure 2. Thermal runaway process of a battery with 100% SOC

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图 3 电池温度与电池温升速率的关系

Figure 3. Battery temperature vs battery temperature rise rate

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图 4 磷酸铁锂电池排气气体组分^[10,22-23]

Figure 4. Vent gas species composition of lithium iron phosphate batteries^[10,22-23]

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图 5 环境温度对H₂/CO/CO₂混合气体爆炸下限的影响

Figure 5. Effect of ambient temperature on lower explosion limit of H₂/CO/CO₂ gas mixtures

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图 6 电池热失控产物与热失控气体爆炸下限对比

Figure 6. Comparison of lower explosion limit between thermal runaway products of batteries and thermal runaway gases

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图 7 不同SOC下电池产气量

Figure 7. Amount of produced vent-gas under different SOCs

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表 1 热失控产物各组分在爆炸下限处的绝热火焰温度

Table 1. Adiabatic flame temperature of each component of the thermal runaway products at their lower explosion limit

环境温度/℃	绝热火焰温度/℃
环境温度/℃	H₂	CO	CH₄	C₂H₄	DMC	60% SOC下热失控产物	80% SOC下热失控产物	100% SOC下热失控产物
25	354.0	1118.4	1207.3	1096.8	1161.0	833.1	792.1	698.6
50	372.5	1144.7	1208.8	1099.4	1163.0	842.5	802.8	710.9
75	363.9	1124.0	1211.0	1102.4	1168.0	841.1	800.1	707.0
100	408.4	1126.5	1211.7	1105.7	1171.0	860.7	821.8	733.5

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