储能用锂离子电池老化过程监测：双层GeTe热电传感器

doi:10.19799/j.cnki.2095-4239.2024.0919

摘要/Abstract

摘要：

储能电池的特性老化衰减及运行状态监督是保障储能电站安全运行的重要手段。本工作开发了一种基于双层GeTe热电材料的储能用锂离子电池老化过程检测及安全预警方法，这种方法利用热电材料两端的温差(ΔT)与热电感应信号之间的关系，能够精确识别电池内部微观层面上的“不可逆反应”。在电池热失控的早期阶段，热电传感器的响应电流可以上升到183.7 μA/μm，比标准工作条件下高出大约十倍，从而有效减少锂离子电池储能系统的异常老化和热失控风险。此外，研究还深入探讨了外部应力对这些双层GeTe热电设备灵敏度和可靠性的影响。研究发现，它们的响应信号对ΔT和温度升高表现出高度的敏感性。具体来说，在电池温差超过60 K之前，传感器的热电响应比率每变化10 K温度梯度就增加超过1.2倍。而且，即使在卷曲应力的影响下，热失控预警信号的强度仍然比正常工作条件下高出5倍以上，显示出设备出色的应力稳定性。研究结果表明，双层GeTe热电材料具有出色的热电传感能力、灵敏度和稳定性，使其成为监测能源存储用锂离子电池老化过程和早期检测热失控事件的有前景的候选材料。

关键词: 储能电池, 早期预警, 双层GeTe, 智能传感

Abstract:

The detection and safety early warning method for lithium-ion battery aging employs double-layer GeTe thermoelectric materials. This method capitalizes on the relationship between the temperature differential (ΔT) across the thermoelectric material and the induced thermoelectric signal to accurately identify "irreversible reactions" at the microscopic level within the battery. During the early stages of thermal runaway, the thermoelectric sensor's response current can surge to 183.7 μA/μm, approximately an order of magnitude higher than standard operating conditions. This significantly reduces the risk of abnormal aging and thermal runaway in lithium-ion battery energy storage systems. The study also evaluated how external stress affects the sensitivity and reliability of these double-layer GeTe thermoelectric devices. Findings have revealed that their response signals are highly sensitive to ΔT and temperature variations. Specifically, before the battery's temperature differential surpasses 60 K, the sensor's thermoelectric response ratio increases by over 1.2 times for every 10 K increment in the temperature gradient. Moreover, even under curling strain, the strength of the thermal runaway early warning signal remains over five times stronger than during normal operating conditions, highlighting the devices' robust stress stability. The findings suggest that double-layer GeTe thermoelectric materials possess excellent thermoelectric sensing capabilities, sensitivity, and stability. These qualities make them a promising solution for monitoring the aging process and enabling early detection of thermal runaway incidents in the energy storage of lithium-ion batteries.

Key words: energy storage battery, early warning, double-layer GeTe, intelligent sensing

中图分类号:

TM 911

李博文, 赵光金, 李雅敏, 杨宵, 张云潇, 董锐锋, 胡玉霞. 储能用锂离子电池老化过程监测：双层GeTe热电传感器[J]. 储能科学与技术, 2025, 14(4): 1352-1361.

Bowen LI, Guangjin ZHAO, Yamin LI, Xiao YANG, Yunxiao ZHANG, Ruifeng DONG, Yuxia HU. Monitoring the aging process of energy storage lithium-ion batteries: Bilayer GeTe thermoelectric sensors[J]. Energy Storage Science and Technology, 2025, 14(4): 1352-1361.

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