石墨与锂金属负极对混合固液锂离子电池短路与针刺安全性的影响

doi:10.19799/j.cnki.2095-4239.2025.0298

摘要/Abstract

摘要：

锂离子电池已广泛应用，但其安全性仍是制约其性能提升和应用拓展的关键。本研究聚焦负极材料对三元软包电池热失控路径的影响，对比石墨与锂金属负极在针刺及外部短路测试中的安全响应。通过同步监测温度、电压、电流等关键参数并结合电池拆解分析，研究发现负极特性从根本上决定了电池的失效机制。在外部短路中，锂金属负极的高反应活性及其循环后表面形成的粉末状沉积锂加剧了副反应放热，导致其瞬时电流（148.7 A vs. 100.9 A）和最高温度（273 ℃ vs. 104 ℃）远超石墨负极，表现出更高的热失控风险。然而，在针刺测试中，锂金属负极却展现出安全优势。针刺造成的局部熔融，以及伴随的物理脱离与快速化学钝化，共同使接触电阻上升至超过40 Ω，有效阻断了持续短路，从而避免热失控。相反，石墨负极因其刚性结构维持短路通路，引发剧烈放热，温度变化速率峰值超过420 ℃/s。本研究揭示了负极材料与热失效行为的构效关系，为通过负极改性开发兼具高能量密度和高安全性的金属锂负极二次电池提供新思路。

关键词: 锂离子电池, 锂金属, 针刺, 短路, 热失控

Abstract:

While lithium-ion batteries are widely adopted, their safety remains a critical bottleneck hindering further advancements. This study investigates how anode materials dictate the thermal runaway pathways of ternary pouch cells, by comparing the safety responses of graphite and lithium metal anodes to nail penetration and external short-circuit tests. By simultaneously monitoring key parameters including temperature, voltage, current and analyzing electrode interface morphology/contact status, this study reveals that anode properties fundamentally dictate the battery's failure mechanisms. In external short-circuit tests, the highly reactive lithium metal anode, combined with powdery lithium deposits formed on its surface after cycling, exacerbates exothermic side reactions, resulting in significantly higher peak currents (148.7 A vs. 100.9 A) and maximum temperatures (273°C vs. 104°C) compared to the graphite anode, indicating a greater thermal runaway risk. Conversely, lithium metal anodes demonstrated safety advantages in nail penetration tests. Localized melting caused by penetration, and the accompanying physical detachment and rapid chemical passivation, together cause the contact resistance to rise above 40 Ω, effectively interrupting the internal short circuit and preventing thermal runaway. In contrast, the rigid graphite structure of graphite anodes maintains the short-circuit path, leading to drastic heat release with a peak temperature rate exceeding 420 °C/s. This study reveals the structure-property-failure relationship between the anode material and thermal failure behavior, providing valuable insights for developing batteries with both high energy density and high safety through anode modification.

Key words: lithium-ion battery, lithium metal, nail penetration, short circuit, thermal runaway

中图分类号:

TM 912

乔荣涵, 桑林, 张中洋, 姚霞银, 刘兴江, 俞海龙. 石墨与锂金属负极对混合固液锂离子电池短路与针刺安全性的影响[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0298.

Ronghan Qiao, Lin Sang, zhongyang Zhang, Xiayin Yao, Xingjiang Liu, Hailong Yu. Graphite vs. Lithium Metal Anodes: Safety of Hybrid Solid-Liquid Lithium Batteries under Short Circuit and Nail Penetration[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0298.

图/表 12

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样品	正极	负极	电压	容量	内阻	测试方法
石墨-短路	NCM811	石墨	2.8~4.2 V	3.6 Ah	7.87 mΩ	短路测试
锂金属-短路	NCM811	锂金属	2.8~4.3 V	3.6 Ah	12.35 mΩ	短路测试
石墨-针刺	NCM811	石墨	2.8~4.2 V	3.6 Ah	11.38 mΩ	针刺测试
锂金属-针刺	NCM811	锂金属	2.8~4.3 V	3.6 Ah	15.14 mΩ	针刺测试

	正极-负极	正极-钢针	钢针-负极
石墨-针刺电池电压	0	0	0
石墨-针刺电池电阻	19.78 Ω	24.52 Ω	4.33 Ω
金属锂-针刺电池电压	4.19 V	4.08 V	0.11 V
金属锂-针刺电池电阻	0.07 Ω	43.57 Ω	42.47 Ω

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