LiMn0.6Fe0.4PO4 过渡金属离子溶出及其对循环性能的影响研究

doi:10.19799/j.cnki.2095-4239.2024.0649

摘要/Abstract

摘要：

通过不同循环周数磷酸锰铁锂(LiMn_0.6Fe_0.4PO₄，LMFP)电池拆解，得到负极Mn、Fe沉积量与循环周数之间的关系，结果表明随着循环周数的增加，LMFP负极Mn沉积量基本呈现线性增加，而负极Fe沉积量保持不变且与磷酸铁锂(LFP)基本同水平。采用扣电比容量恢复率测试、XRD及EIS测试进行循环初期(BOL)和循环末期(EOL)正、负极片性能表征，结果表明，LMFP循环过程中正极材料结构相对稳定，容量损失主要发生在负极。LMFP正极溶出的少量Mn²⁺迁移并沉积至负极，催化电解液和锂盐分解，导致大量活性锂损失，同时负极阻抗增加，最终表现出循环容量明显衰减。

关键词: 磷酸锰铁锂, 过渡金属离子溶出, 循环性能, 活性锂损失, 界面化学

Abstract:

∶By disassembling lithium ferric manganese phosphate (LMFP) batteries with different cycles, the relationship between the deposition of Mn and Fe in the negative electrode and the cycle was obtained. The results showed that the deposition of Mn in the negative electrode of LMFP increased linearly with the increase of cycles, while the deposition of Fe in the negative electrode remained unchanged and was at the same level as that of lithium iron phosphate (LFP). The properties of positive and negative electrodes at the beginning of the cycle life (BOL) and the end of the cycle life (EOL) were characterized using the capacity recovery test, X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS). The results showed that the structure of LMFP cathode material is relatively stable during the cycle, and the capacity loss primarily occurs in the negative electrode. A small amount of Mn²⁺ dissolved from the positive electrode of LMFP migrates and deposits to the negative electrode, catalyzing the decomposition of electrolytes and lithium salt and resulting in a large amount of active lithium loss. Simultaneously, the negative electrode impedance increases and finally shows a significant decline in circulation capacity.

Key words: lithium ferric manganese phosphate, dissolution of transition metal ions, cycle performance, active lithium loss, interface chemistry

中图分类号:

TQ 152

刘范芬, 吴婷婷, 温圣耀, 高建行, 陈勐, 李迟. LiMn_0.6Fe_0.4PO₄ 过渡金属离子溶出及其对循环性能的影响研究[J]. 储能科学与技术, 2025, 14(1): 13-20.

Fanfeng LIU, Tingting WU, Shengyao WEN, Jianhang GAO, Meng CHEN, Chi LI. A study on dissolution of transition metal ions and influence on the cycling performance of LiMn_0.6Fe_0.4PO₄[J]. Energy Storage Science and Technology, 2025, 14(1): 13-20.

图/表 10

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样品	a/nm	b/nm	c/nm	V/nm³
LMFP-BOL	0.47249	1.04053	0.60646	0.29816
LMFP-EOL	0.47221	1.04018	0.60621	0.29776

石墨负极参数	BOL极片(25 ℃)	EOL极片(25 ℃)
充电比容量/(mAh/g)	334.2	314.7
放电比容量/(mAh/g)	315.9	291.2

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LiMn_0.6Fe_0.4PO₄ 过渡金属离子溶出及其对循环性能的影响研究

A study on dissolution of transition metal ions and influence on the cycling performance of LiMn_0.6Fe_0.4PO₄

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参考文献 24

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LMFP正极	循环周数	负极Mn沉积量/ppm	负极Fe沉积量/ppm
LMFP-1	BOL	4	13
	100周	44	16
	200周	60	18
	400周	84	18
	600周	91	53
	EOL	130	51
LMFP-2	BOL	7	15
	100周	35	17
	200周	54	19
	400周	87	25
	600周	106	55
	800周	118	28
	EOL	179	21

LFP正极	负极Fe沉积量/ppm
LFP正极	200周	500周	1000周	2000周
LFP-1	9	24	12	21
LFP-2	17	36	25	40
LFP-3	13	31	22	44