Application of titration gas chromatography technology in the quantitative detection of lithium plating in Li-ion batteries

doi:10.19799/j.cnki.2095-4239.2022.0117

Abstract

Abstract:

Lithium plating is induced in lithium-ion batteries during fast charging, resulting in severe capacity fading and possible safety issues. Therefore, the accurate detection of lithium plating is vital for the safe operation of lithium-ion batteries. This study explored the application of titration gas chromatography (TGC) quantitatively detect lithium plating in lithium-ion batteries. The TGC can accurately detect the amount of plated lithium on the graphite anode, with a detection limit of 2.4 μmol Li. First, the relationship between H₂concentration and H₂ signal area detected using TGC was calibrated using a standard gas of known concentration. The feasibility of the experimental device was further analyzed through tests on samples containing different lithium metal contents, which demonstrated that the developed detection system could quantitatively detect lithium plating, and the relationship between the amount of metallic lithium and the H₂ concentration detected using TGC was determined. Moreover, the amount of plated lithium on the anode detected using the TGC method was consistent with the results measured by nuclear magnetic resonance, demonstrating the TGC method's high accuracy. Finally, the TGC method was used to detect the amount of plated lithium within two 1 Ah lithium-ion batteries after low-temperature charging. The results were consistent with the amount of plated lithium estimated from battery capacity loss, with errors less than 7%. This study demonstrates that the TGC method can be used to quantitatively detect lithium plating in lithium-ion batteries and that it has the advantages of low cost, feasibility, and scalability.

Key words: lithium-ion battery, lithium plating detection, titration gas chromatography, nuclear magnetic resonance

CLC Number:

TM 912.9

Tao SUN, Tengteng SHEN, Xin LIU, Dongsheng REN, Jinhai LIU, Yuejiu ZHENG, Luyan WANG, Languang LU, Minggao OUYANG. Application of titration gas chromatography technology in the quantitative detection of lithium plating in Li-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(8): 2564-2573.

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样品	参数	厂家数据	单位
单体	容量@1/3C	1	Ah
	反应面积	4.35×10^-2	m²
	上限电压	4.2	V
	下限电压	3.0	V
负极	材料	graphite	—
	颗粒直径	7.1	μm
	孔隙率	0.318	1
正极	材料	Li _x Ni_0.5Co_0.2Mn_0.3O₂	—
	颗粒直径	3.2	μm
	孔隙率	0.313	1
隔膜	孔隙率	0.4	1

测试参数	设置
拉莫频率	232.76 MHz
脉冲宽度	1.6 s
延迟时间	20 s
旋转频率	15 kHz
扫描次数	16
扫描范围	-500～500 ppm

序号	Li质量/mg	反应容器/mL	测试样品 Li摩尔量/mol	理论H₂浓度/(mol/L)	GC谱图特征峰面积			GC测试 H₂浓度/(mol/L)
1	1.2	587	1.73×10^-4	1.49×10^-4	12560	12610	12630	1.64×10^-4
2	3.3	587	4.76×10^-4	4.09×10^-4	31434	33021	33577	4.25×10^-4
3	4.7	587	6.77×10^-4	5.82×10^-4	47979	48250	48009	6.25×10^-4
4	7.0	587	1.009×10^-3	8.67×10^-4	68899	69024	68968	8.97×10^-4
5	10.7	1124	1.542×10^-3	6.89×10^-4	52100	51596	52001	6.75×10^-4

序号	Li质量/mg	LiCl质量/mg	Li质量比/%	LiCl质量比/%	测试粉末质量/mg	测试样品Li摩尔量/mol	NMR谱图特征峰面积
1	2.3	500.4	0. 4575	99.5425	0.06343	4.15E-05	0.056606
2	5.1	499.0	1.0117	98.9883	0.06168	8.91E-05	0.126313
3	8.4	500.0	1.6522	98.3478	0.06441	0.000152	0.182615
4	9.9	500.7	1.9389	98.0611	0.06447	0.000179	0.226653
5	14.7	501.4	2.8483	97.1517	0.06537	0.000266	0.297649

样品序号	TGC测试析锂量 /(mol/g)	NMR测试析锂量 /(mol/g)	误差/%
1	2.10×10^-3	2.11×10^-3	0.5
2	1.53×10^-3	1.64×10^-3	7.2
3	1.73×10^-3	1.84×10^-3	6.4