锂离子电池高温贮存容量衰减分析

doi:10.19799/j.cnki.2095-4239.2021.0614

摘要/Abstract

摘要：

为了探究锂离子电池高温贮存后的容量衰减因素，研制了额定容量1.6 Ah的18650锂离子电池，并且负极采用预锂化技术。对比分析了电池常温及70 ℃分别满电贮存5个月后的容量损失、恢复容量、微分容量、电化学阻抗谱、形貌、结构、元素含量及热分析等。结果表明，电池70 ℃搁置后放电容量仅为25 ℃搁置后容量的79.14%，其中可逆容量损失占比为52.8%。电池的不可逆容量衰降源于严重的正负极失衡，其中未预锂化电池主要为负极损失，而预锂化电池由于负极锂过量主要表现为正极损失。70 ℃搁置电池内阻更高，特别是负极增加明显。70 ℃负极表面更多的“死锂”，更高的氧含量，意味着表面更多的副反应。此外，高温搁置并未对材料结构造成影响。

关键词: 高温贮存, 容量衰减, 自放电, 预锂化, 锂离子电池

Abstract:

A 1.6 Ah 18650 lithium-ion nominal capacity battery with a prelithiation process was developed to determine the capacity fading factors of lithium-ion batteries after high-temperature storage. Comparative analysis of the capacity loss, capacity recovery, dQ/dV, EIS, SEM, XRD, EDS, ICP, and thermal analysis of the battery storage under RT and 70 ℃ after five months at 100% SOC, respectively. The results demonstrate that the battery's discharge capacity at 70 ℃ is only 79.14% of its capacity at 25 ℃, and the reversible capacity loss accounts for 52.8%. The irreversible capacity loss is primarily due to the severe imbalance between the cathode and anode. The nonprelithium battery is subjected to anode fading, whereas the prelithium battery undergoes cathode fading due to the excessive lithium in the anode. Furthermore, the internal resistance of the battery storage under 70 ℃ is greater than that under 25 ℃, particularly when the anode quantity increases. There is significantly more "dead lithium" on the surface of the anode for the battery storage under 70 ℃ and more oxygen content was observed, meaning more side reactions on the surface. Moreover, high-temperature storage did not affect the structure of the electrode materials.

Key words: high temperature storage, capacity fading, self-discharge, prelithiation, lithium-ion battery

中图分类号:

TM 912.9

程广玉, 刘新伟, 梅悦旎, 顾洪汇, 杨丞, 王可. 锂离子电池高温贮存容量衰减分析[J]. 储能科学与技术, 2022, 11(5): 1339-1349.

Guangyu CHENG, Xinwei LIU, Yueni MEI, Honghui GU, Cheng YANG, Ke WANG. Capacity fading analysis of lithium-ion battery after high temperature storage[J]. Energy Storage Science and Technology, 2022, 11(5): 1339-1349.

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温度	Chi squared	R_S/mΩ	R_sf/mΩ	R_ct/mΩ
25 ℃	2.024e-04	18.66	6.098	8.922
70 ℃	5.187e-04	20.56	19.3	17.7

元素	25 ℃		70 ℃
元素	质量比/%	原子比/%	质量比/%	原子比/%
C K	60.96	68.14	47.32	41.52
O K	32.19	27.01	6.86	5.07
F K	6.86	4.84	0.19	0.10
Al K	—	—	45.62	53.31
总量	100.00	100.00	100.00	100.00

项目	a/Å	c/Å	d002/nm
25 ℃搁置	2.461	6.713	0.3357
70 ℃搁置	2.467	6.695	0.3347

项目	a/Å	c/Å	c/a	I(003)/I(104)
25 ℃搁置	2.8582	14.1806	4.96	1.102
70 ℃搁置	2.8583	14.1826	4.96	1.520

项目		Al	Co	Ni
25 ℃正极	浓度/(mg/L)	1.183	6.24	38.58
25 ℃正极	化学计量比	0.054328	0.131198	0.814474
70 ℃正极	浓度/(mg/L)	1.662	6.74	39.47
70 ℃正极	化学计量比	0.072601	0.134796	0.792603
25 ℃负极	浓度/(mg/L)	—	—	—
70 ℃负极	浓度/(mg/L)	0.103	—	—