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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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

Received: 12 December 2022

PACS:

TM912

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	Su Lei
	Yu Jiachuan
	Yang Fan
	Yang Zhichun
	Zhang Cheng

Cite this article:

Su Lei,Yu Jiachuan,Yang Fan等. Study on Characteristic Parameters of LFP Battery under the Condition of Overcharge Thermal Failure[J]. Transactions of China Electrotechnical Society, 2023, 38(21): 5913-5922.

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https://dgjsxb.ces-transaction.com/EN/10.19595/j.cnki.1000-6753.tces.222303 OR https://dgjsxb.ces-transaction.com/EN/Y2023/V38/I21/5913

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