磷酸铁锂锂离子电池低温不可逆析锂及其对电池性能衰减的影响

doi:10.19799/j.cnki.2095-4239.2024.0285

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (10): 3656-3665.doi: 10.19799/j.cnki.2095-4239.2024.0285

磷酸铁锂锂离子电池低温不可逆析锂及其对电池性能衰减的影响

李义函(), 卢世刚(), 王晶, 查汪珺, 戴正航, 郭奕彤, 杨泽茜

上海大学，上海 200000

收稿日期:2024-04-01 修回日期:2024-04-18 出版日期:2024-10-28 发布日期:2024-10-30
通讯作者: 卢世刚 E-mail:liyihansolar@163.com;slu@shu.edu.cn
作者简介:李义函（1999—），女，硕士，研究方向为锂离子电池，E-mail：liyihansolar@163.com；
基金资助:
国家电网有限公司科技项目资助(5500-202255364A-2-0-ZN)

Effect of irreversible lithium plating at low temperature on the performance degradation of LiFePO₄ lithium-ion batteries

Yihan Li(), Shigang LU(), Jing WANG, Wangjun ZHA, Zhenghang DAI, Yitong GUO, Zexi YANG

Shanghai University, Shanghai 200000, China

Received:2024-04-01 Revised:2024-04-18 Online:2024-10-28 Published:2024-10-30
Contact: Shigang LU E-mail:liyihansolar@163.com;slu@shu.edu.cn

摘要/Abstract

摘要：

锂离子电池低温充放电过程中发生锂的析出-溶解反应，由于不可逆析锂导致生成“死锂”，对电池性能造成影响。本工作研究了磷酸铁锂锂离子电池在5~-12 ℃范围内0.1C充放电过程中锂的析锂-溶解行为，建立了总析锂量和可逆析锂量、不可逆析锂量与充放电温度之间的关联关系；拆解低温充放电后的电池，采用SEM、EDX和XPS分析了负极的形貌、元素分布和表面组成，明确了“死锂”在负极表面/内部的分布特征；研究了低温充放电后电池的充放电性能和循环性能，发现低温充放电后电池容量降低，5 ℃充放电后电池较原始样品0.5C循环容量衰减更快，而更低温度充放电后电池循环性能变好。研究得出，电池充放电温度越低，总析锂容量越高且不可逆析锂容量占比越大，而低温充放电后电池容量降低主要归因于不可逆析锂导致的活性锂损失，更低温度下充放电后电池循环性能更好归因于活性锂损失造成负极嵌脱锂最低电位的升高，而5 ℃时循环性能变差则归因于负极元素分布、孔隙结构和表面组成的改变。

关键词: 磷酸铁锂锂离子电池, 低温充放电, 不可逆析锂, 负极形貌与元素分布, 性能衰减

Abstract:

During the low-temperature charging and discharging of lithium-ion batteries, lithium plating and stripping occur, with irreversible lithium plating leading to the formation of "dead lithium". This phenomenon adversely affects the battery's electrochemical performance. This study investigates the lithium plating-stripping behavior of commercial batteries, using LiFePO₄ as the cathode and graphite as the anode, during 0.1C charge-discharge cycles at temperatures from 5 to -12 ℃. A correlation between total and reversible lithium plating was established at different charging and discharging temperatures. Analysis of disassembled batteries, including negative electrode samples analyzed by SEM, EDX and XPS, revealed insights into the morphology, elemental distribution, and surface composition, clarifying the distribution of "dead lithium" on and within the negative electrodes. The study also assessed the impact of low-temperature charging and discharging on battery performance. It was found that the batteries' discharge capacities decreased following low-temperature cycling. At 0.5C, capacity degradation was more rapid after cycling at 5 ℃ compared to the primary battery, but slower at temperatures lower than 5 ℃. We conclude that with lower temperatures increase both the total amount of lithium plating and the irreversible portion. The irreversible plating leads to a loss of active lithium, reducing capacity. However, at temperatures below 5℃, the increased loss of active lithium results in a lower negative electrode potential during lithiation, slowing the following capacity fading. The worse cycling performance at 5℃ is attributed to changes in the negative electrode's element distribution, pore structure, and surface composition.

Key words: lithium ion battery with the LiFePO₄ cathode, charging and discharging at low temperature, irreversible lithium loss, morphology and element distribution within graphite electrode, performance degradation

中图分类号:

TM 911

李义函, 卢世刚, 王晶, 查汪珺, 戴正航, 郭奕彤, 杨泽茜. 磷酸铁锂锂离子电池低温不可逆析锂及其对电池性能衰减的影响[J]. 储能科学与技术, 2024, 13(10): 3656-3665.

Yihan Li, Shigang LU, Jing WANG, Wangjun ZHA, Zhenghang DAI, Yitong GUO, Zexi YANG. Effect of irreversible lithium plating at low temperature on the performance degradation of LiFePO₄ lithium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(10): 3656-3665.

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温度	CE/%	可逆析锂容量/Ah	不可逆析锂容量/Ah	可逆析锂/总析锂	不可逆析锂/总析锂
5 ℃	98.94	0.5398	0.0711	88.36%	11.64%
-5 ℃	93.09	2.8948	0.4242	87.22%	12.78%
-8 ℃	91.37	3.2208	0.5004	86.56%	13.45%
-10 ℃	89.57	3.3939	0.5729	85.56%	14.44%
-12 ℃	86.99	3.2236	0.6815	82.55%	17.45%

元素	5 ℃/%(原子百分数)	-12 ℃/%(原子百分数)
C1s	92.68	88.56
F1s	0.78	0.92
Li1s	1.60	4.38
O1s	4.72	5.80
P2p	0.22	0.34

磷酸铁锂锂离子电池低温不可逆析锂及其对电池性能衰减的影响

Effect of irreversible lithium plating at low temperature on the performance degradation of LiFePO₄ lithium-ion batteries

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磷酸铁锂锂离子电池低温不可逆析锂及其对电池性能衰减的影响

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