磷酸铁锂储能电池过充热失效特征参量研究

doi:10.19595/j.cnki.1000-6753.tces.222303

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摘要锂电池的安全性,是掣肘锂电池储能技术发展的重要问题。为探究锂电池过充热失效的特征参量,采用两段式充电对100 A·h磷酸铁锂储能电池展开过充实验。通过检测特征气体、电压、温度等参量,对热失效早期锂电池行为进行了研究,并对停止过充后锂电池的风险状况进行了分析。气体检测仪和气相色谱仪检测结果表明,H₂为出现最早且含量最高的气体,在特征气体中占比达到62%以上,能够在热失效前至少3 min完成预警,最适合作为预警气体;其次为CO和烃类气体,烃类气体中C₂H₄含量最高,达到烃类气体总量的78.5%。分段式充电结果表明,在锂电池发生热失效前的电压迅速上升期停止充电,能避免热失效发生。停止过充后电池表面温度仍会继续上升,说明电池内部副反应放热仍在继续,可能促使热失效的发生。

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关键词 ：磷酸铁锂电池, 热失效, 气相色谱, 气体预警

Abstract：The safety of lithium-ion battery energy storage is an important issue that hinders the development of lithium battery energy storage power stations. A lithium battery overcharge experimental platform was built to explore the characteristic parameters of overcharge thermal failure of lithium batteries. The overcharge experiment of 100 A·h lithium iron phosphate (LFP) battery was conducted by step charging. By detecting the characteristic gas, voltage, temperature, etc., the behaviors of lithium batteries at the early stage of thermal failure were studied, and the risk of lithium batteries after a power failure was analyzed. The experimental platform simulates the internal structure of the Lithium battery energy storage power station, and the experimental data obtained can provide a basis for the safety warning design of the lithium battery energy storage system.
The experimental results show that during the period from overcharge to thermal failure of lithium battery, the battery shell will expand, the temperature will rise, the voltage will rise in stages, the gas will gush out, and smoke and other phenomena will occur. The detection results of the gas detector and gas chromatograph show that the characteristic gases generated by overcharge and thermal failure of lithium iron phosphate battery include H₂O, CO, hydrocarbon gases, etc. Among them, H₂ appears the earliest and accounts for the highest proportion, reaching more than 62% of the characteristic gas content at the peak, and CO and H₂ appear almost simultaneously. Hydrocarbon gas appears later, with the highest ethylene content, accounting for 78.5% of the total content at the peak. The pre-test showed that the voltage would reach the critical value of 20 V in a short time before the thermal failure. Therefore, this critical value is selected as the segmentation point for the segmented overcharge. The experimental results show that stopping overcharging at this critical value can successfully prevent the occurrence of thermal failure, but the safety state of the battery would not improve significantly in a short time (half an hour in this experiment), and thermal failure will occur soon after secondary charging. The temperature detection results show that the temperature of the battery will continue to rise in a short time after the overcharge is stopped, which may lead to the melting of the lithium battery diaphragm and thermal failure. Combined with the internal side reaction of lithium battery, it can be found that the lithium dendrite and electrolyte reaction provides O₂ for the subsequent reaction and the heat required to maintain the reaction. Whether the battery temperature rises after stopping charging is related to the amount of residual lithium dendrite in the battery. It can be inferred from the chemical reaction inside the battery that whether the lithium battery will have thermal failure after a power failure is related to the lithium dendrite content inside the battery.
Based on the above experimental results, before the safety valve is opened, the voltage warning can be set in the first voltage rise period (3.65~5.06 V). After the safety valve is opened, H₂ and CO can be used as the first-level warning, the hydrocarbon gas appearing later can be set as the second- level warning. In the second voltage rise period (4.85~20 V), the voltage can be set as the third-level warning.

Key words： LFP battery thermal failure gas chromatography gas warning

收稿日期: 2022-12-12

PACS:

TM912

基金资助:国网湖北省电力有限公司科技项目资助（B3153221001F）

通讯作者: 余嘉川男,1997年生,硕士研究生,研究方向为高压放电与等离子体应用。E-mail：yujiachuan@mail.iee.ac.cn

作者简介: 宿磊男,1989年生,硕士,研究方向为配电自动化与电气火灾防治。E-mail：sulei@me.com

引用本文:

宿磊, 余嘉川, 杨帆, 杨志淳, 章程. 磷酸铁锂储能电池过充热失效特征参量研究[J]. 电工技术学报, 2023, 38(21): 5913-5922. Su Lei, Yu Jiachuan, Yang Fan, Yang Zhichun, Zhang Cheng. Study on Characteristic Parameters of LFP Battery under the Condition of Overcharge Thermal Failure. Transactions of China Electrotechnical Society, 2023, 38(21): 5913-5922.

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