A study on dissolution of transition metal ions and influence on the cycling performance of LiMn0.6Fe0.4PO4

doi:10.19799/j.cnki.2095-4239.2024.0649

Abstract

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

CLC Number:

TQ 152

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.

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References 24

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

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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