过充电触发的LFP和NCM锂离子电池的热失控行为：差异与原因

doi:10.19799/j.cnki.2095-4239.2021.0548

摘要/Abstract

摘要：

软包锂离子电池相比较于硬壳电池具有更高的能量密度，由于特殊的电池结构软包锂离子电池具备特殊的热失控行为和规律。本工作研究了以磷酸铁锂(LFP)和镍钴锰酸锂(NCM)材料为正极的两种软包锂离子电池在不同的倍率(0.5～3 ?C)电流下过充电后的失效和热失控行为，分析了电池的质量损失、失效电压、电池温升方面的差异。结果表明，LFP和NCM电池在过充电后均会因发生副反应生成气体导致铝塑膜外壳破裂，1 C倍率电流下LFP电池在充电至133.4%带电状态(SOC)时发生破裂，并导致电池失效，而NCM电池在充电至143.8% SOC时破裂，随后诱发热失控和着火。电池破裂电压均随充电倍率的增加(0.5～3 C)而呈现先增大后减小的趋势，在1.5 C时破裂电压最高，LFP电池的破裂电压高于NCM电池。此外，LFP和NCM电池的质量损失范围分别为2.07%～5.82%和28.51%～36.75%，随充电倍率变化不明显。研究还揭示了LFP和NCM电池过充电过程中温度升高的不同阶段特征，并从材料分子结构的角度对该差异的原因进行了分析。研究结果可为新能源汽车用锂电池单体选型提供参考。

关键词: 软包锂离子电池, 失效, 热失控, 过充电, 磷酸铁锂, 镍钴锰酸锂

Abstract:

Compared with hardshell batteries, pouch-type lithium-ion batteries (LIBs) have the qualities of higher energy density, causing unique thermal runaway behaviors and hazards due to their special structures. In this work, two types of LIB variations with lithium iron phosphate (LFP) and lithium nickel cobalt manganese oxide (NCM) based cathodes are experimentally investigated for failure, thermal runaway behaviors, mass loss, rupture voltage, and temperature rise after being over-charged at various current-rates (0.5～3 C). The results show that the aluminum plastic shell ruptures for LFP and NCM LIBs due to pressure accumulation inside due to side reactions during overcharging. Specifically, the LFP battery ruptures and fails when charged to a 133.4% state of charge (SOC), while the NCM battery ruptures after thermal runaway and fires when charged to about 143.8% SOC. With the increase of current rate, the rupture voltage of LIBs firstly increases and then decreases. The rupture voltage is the highest at 1.5 C, and the rupture voltages of LFP batteries are higher than those of the NCM batteries. In addition, the mass loss of LFP and NCM batteries ranges from 2.07% to 5.82% and 28.51% to 36.75%, respectively, independent of the current rate. The various characteristics of temperature rise in LFP and NCM batteries during overcharge are also revealed, and the reasons for this difference are analyzed from the perspective of the molecular structure of cathode materials. The results of this study could provide references for the selection of LIBs for electric vehicles.

Key words: pouch-type lithium-ion batteries, failure, thermal runaway, over-charging, lithium iron phosphate, lithium nickel cobalt manganese oxide

中图分类号:

TM 912

李磊, 李钊, 姬丹, 牛慧昌. 过充电触发的LFP和NCM锂离子电池的热失控行为：差异与原因[J]. 储能科学与技术, 2022, 11(5): 1419-1427.

Lei LI, Zhao LI, Dan JI, Huichang NIU. Overcharge induced thermal runaway behaviors of pouch-type lithium-ion batteries with LFP and NCM cathodes： the differences and reasons[J]. Energy Storage Science and Technology, 2022, 11(5): 1419-1427.

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参考文献 23

1	SCROSATI B, HASSOUN J, SUN Y K. Lithium-ion batteries. A look into the future[J]. Energy & Environmental Science, 2011, 4(9): 3287-3295. .
2	RITCHIE A, HOWARD W. Recent developments and likely advances in lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 809-812.
3	SUN P, BISSCHOP R, NIU H, et al. A review of battery fires in electric vehicles[J]. Fire Technology, 2020, 56(4): 1361-1410.
4	LI Z, NIU H, JIANG X. Simulation of electrical abuse of high-power lithium-ion batteries[J]. Energy Procedia, 2017, 142: 3468-3473.
5	马天翼, 王芳, 徐大鹏, 等. 动力电池轻度电滥用积累造成的性能和安全性劣化研究[J]. 储能科学与技术, 2020, 9(2): 400-408.
	MA T, WANG F, XU D, et al. Investigation of the performance and safety degradation caused by slight accumulation of electricity in traction batteries[J]. Energy Storage Science and Technology, 2020, 9(2): 400-408.
6	陈才星, 牛慧昌, 陆瑞强, 等. 基于三维分层结构的锂离子电池电化学-热耦合仿真及极耳优化[J]. 储能科学与技术, 2020, 9(3): 831-839.
	CHEN C X, NIU H C, LU R Q, et al. Electrochemical-thermal coupled simulation and tab optimization of lithium ion battery based on three-dimensional multi-layer structure[J]. Energy Storage Science and Technology, 2020, 9(3): 831-839.
7	ZENG Y Q, WU K, WANG D Y, et al. Overcharge investigation of lithium-ion polymer batteries[J]. Journal of Power Sources, 2006, 160(2): 1302-1307.
8	KERMANI G, SAHRAEI E. Review: characterization and modeling of the mechanical properties of lithium-ion batteries[J]. Energies, 2017, 10(11): 1730.
9	李钊, 陈才星, 牛慧昌, 等. 锂离子电池热失控早期预警特征参数分析[J]. 消防科学与技术, 2020, 39(2): 146-149.
	LI Z, CHEN C X, NIU H C, et al. Characteristic parameter analysis of thermal runaway early warning of lithium-ion battery[J]. Fire Science and Technology, 2020, 39(2): 146-149.
10	陈才星, 牛慧昌, 李钊, 等. 环氧树脂板对锂离子电池热失控扩展的阻隔作用[J]. 储能科学与技术, 2019, 8(3): 532-537.
	CHEN C X, NIU H C, LI Z, et al. Thermal runaway propagation mitigation of lithium ion battery by epoxy resin board[J]. Energy Storage Science and Technology, 2019, 8(3): 532-537.
11	NIU H C, CHEN C X, JI D, et al. Thermal-runaway propagation over a linear cylindrical battery module[J]. Fire Technology, 2020, 56(6): 2491-2507.
12	LIU Y H, NIU H C, LI Z, et al. Thermal runaway characteristics and failure criticality of massive ternary Li-ion battery piles in low-pressure storage and transport[J]. Process Safety and Environmental Protection, 2021, 155: 486-497.
13	WANG Q S, PING P, ZHAO X J, et al. Thermal runaway caused fire and explosion of lithium ion battery[J]. Journal of Power Sources, 2012, 208: 210-224.
14	FENG X N, OUYANG M G, LIU X, et al. Thermal runaway mechanism of lithium ion battery for electric vehicles: A review[J]. Energy Storage Materials, 2018, 10: 246-267.
15	任东生, 冯旭宁, 韩雪冰, 等. 锂离子电池全生命周期安全性演变研究进展[J]. 储能科学与技术, 2018, 7(6): 957-966.
	REN D S, FENG X N, HAN X B, et al. Recent progress on evolution of safety performance of lithium-ion battery during aging process[J]. Energy Storage Science and Technology, 2018, 7(6): 957-966.
16	BELOV D, YANG M H. Investigation of the kinetic mechanism in overcharge process for Li-ion battery[J]. Solid State Ionics, 2008, 179(27/28/29/30/31/32): 1816-1821.
17	FERNANDES Y, BRY A, DE PERSIS S. Identification and quantification of gases emitted during abuse tests by overcharge of a commercial Li-ion battery[J]. Journal of Power Sources, 2018, 389: 106-119.
18	OUYANG D X, LIU J H, CHEN M Y, et al. Investigation into the fire hazards of lithium-ion batteries under overcharging[J]. Applied Sciences, 2017, 7(12): 1314.
19	美)詹姆士 G. 昆棣瑞(James G. Quintiere著.杜建科,王平,高亚萍译. 火灾学基础[M]. 北京: 化学工业出版社, 2010.
20	REN D S, FENG X N, LU L G, et al. Overcharge behaviors and failure mechanism of lithium-ion batteries under different test conditions[J]. Applied Energy, 2019, 250: 323-332.
21	MAHNE N, RENFREW S E, MCCLOSKEY B D, et al. Electrochemical oxidation of lithium carbonate generates singlet oxygen[J]. Angewandte Chemie International Edition, 2018, 57(19): 5529-5533.
22	BAK S M, HU E Y, ZHOU Y N, et al. Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy[J]. ACS Applied Materials & Interfaces, 2014, 6(24): 22594-22601.
23	SCHIPPER F, ERICKSON E M, ERK C, et al. Review—recent advances and remaining challenges for lithium ion battery cathodes[J]. Journal of the Electrochemical Society, 2016, 164(1): A6220-A6228.

电池	正极	负极	电解液	电压U	容量C	尺寸
1	LFP	石墨	EC∶DMC∶DEC∶EMC 29∶5∶14∶34.5	3.2 V	3 Ah	9.6 mm×65 mm×90 mm(厚×宽×长)
2	NCM(5∶2∶3)	石墨	EC∶DMC∶EMC 30∶13∶41.5	3.7 V	4.5 Ah	8.0 mm×60 mm×100 mm(厚×宽×长)

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