锂离子电池内部信号监测技术概述

doi:10.19799/j.cnki.2095-4239.2024.0093

摘要/Abstract

摘要：

锂离子电池在便携式电子产品、储能电站和电动汽车等领域得到了广泛的应用。然而，在电池容量不断上升的同时，锂离子电池的热失控风险也在增加，进而带来安全问题。现有的电池管理系统通过监测电池表面温度以及端电压来判断电池的健康状况。但是研究发现由于电池组件的多层结构和较差的导热性，电池内部温度、气体等很难散发到外部，导致对电池表面温度等外部信号的监测存在时效性差的问题。因此人们尝试直接监测电池内部温度、压力、应变和气体等信号的变化情况，实现及时预警电池热失控，增强锂离子电池在不同应用场景下的安全性。本文在理解热失控机制的基础上，概述了可以监测电池内部信号的方法。总结了锂离子电池在发生热失控时涉及的一系列放热反应，及在这些反应过程中电池内部温度、压力和气体等信号的变化情况。对于能够直接监测电池内部信号的技术，主要介绍了电化学阻抗分析和内置传感器监测，为以后优化监测方法提供参考信息。其中，将传感器植入到电池内部在实际应用中具有良好的前景。为了进一步提高锂离子电池系统的安全性，本文还对未来可能的研究方向进行了展望。

关键词: 锂离子电池, 热失控, 内部信号, 监测和预警

Abstract:

Lithium-ion batteries are extensively used in portable electronics, energy storage systems, and electric vehicles. However, with the increasing capacity of these batteries, the risk of thermal runaway and associated safety concerns have escalated. Traditional battery management systems primarily focus on monitoring surface temperature and terminal voltage to assess battery health. Yet, the multilayer structure and poor thermal conductivity of battery modules make it challenging to effectively monitor internal temperature and gas distribution, leading to delayed detection of critical signals such as surface temperature variations. Consequently, there is a growing emphasis on monitoring changes in internal temperature, pressure, strain, and gas signals to provide timely warnings of battery thermal runaway and enhance safety across various applications. This review offers a comprehensive examination of the mechanisms of thermal runaway in lithium-ion batteries and the techniques for monitoring internal battery signals. It highlights a series of exothermic reactions associated with thermal runaway, along with the resulting changes in internal temperature, pressure, and gas signals. Moreover, the review discusses monitoring techniques that directly assess internal battery signals, such as electrochemical impedance spectroscopy and embedded sensor monitoring, offering insights for the optimization of future monitoring methods. The practical applications and potential of embedded sensors within batteries are emphasized, along with the prospects for further enhancing the safety of lithium-ion battery systems.

Key words: lithium-ion battery, thermal runaway, internal battery signals, monitoring and early warning

中图分类号:

TM 911

王玉婷, 李秋桐, 胡一鸣, 郭新. 锂离子电池内部信号监测技术概述[J]. 储能科学与技术, 2024, 13(4): 1253-1265.

Yuting WANG, Qiutong LI, Yiming HU, Xin GUO. Techniques for monitoring internal signals of lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(4): 1253-1265.

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传感器类型	传感器尺寸	验证电池	嵌入方法	响应时间 /灵敏度	稳定性	电池容量	参考文献
热阻式	4 mm×5 mm	CR2032纽扣电池	借助3D打印的聚合物基板	5 s/3.883 Ω/℃	—	影响较小可忽略	[44]
热阻式	310 μm×620 μm	纽扣电池正极：磷酸铁锂负极：氧化钛锂	借助柔性聚酰亚胺薄膜衬底，构筑薄膜温度传感器	—	好	下降10.32%	[45]
热阻式	单个测量位点5 mm×5 mm，一共7个	软包电池正极：镍钴锰酸锂负极：石墨	用N-甲基吡咯烷酮溶剂在正极上去除小面积的活性物质	—	100次循环后测得的温度无明显差异	最初下降20%，循环500次之后并无明显下降	[46]
热电偶	0.5 mm (带绝缘层)	软包电池正极：锰酸锂负极：石墨	制造过程中，多个热电偶嵌入在层压电池的电极层之间	485～620 s	几个月内仍可使用	忽略	[49]
光纤传感器	直径125 μm，长12 mm	商用18650 正极：磷酸铁锂负极：石墨	电池负极的中心位置钻了一个1 mm的孔	10.3 pm/℃	热失控前后仍具有出色的再现性	100次循环后下降20%	[61]

监测技术	优点	缺点
EIS	无需复杂硬件即可预测电池内部温度；热失控预测精度高；在线预测电池状态，与BMS无缝耦合	未能快速有效地监测大型电池；由于不同的锂离子电池系统阻抗参数不同，校准过程复杂；测试仪器较大，成本较高
内置式温度传感器	直接提供准确的电池内部温度，实现电池热失控精准预测	热阻式温度传感器监测温度范围较低；热电偶响应时间较长；光纤传感器对电池包装要求较高，且易受弯曲和振动的影响
内置式应变传感器	为快速准确分析阳极材料、内部应变分布、胶辊尺寸等因素对LIBs安全性的影响提供了一个平台	易受干扰；目前的应变传感器会破坏电池结构
内置式压力传感器	电池的荷电状态、工作温度等因素都会影响电池内部气压。实时监测电池内部气压的变化，对于了解电池的健康状况具有重要意义	现有的气压监测装置体积较大，应用困难
内置式气体传感器	热失控检测精度高、速度快；简单可行、易于实现、成本低；易于与BMS接口连接；可以探究电池内部气体衍化行为，为判断电池副反应提供依据	无法预测电池的状态；潜在的传感器故障，如气体交叉干扰和气体传感器中毒

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