Effects of sulfur-containing electrolyte additives on the performance of lithium nickel cobalt manganese oxide//graphite Li-ion batteries

doi:10.19799/j.cnki.2095-4239.2023.0250

Abstract

Abstract:

The effects of six electrolyte additives: vinylene carbonate (VC), ethylene sulfite (ES), ethylene sulfate (DTD), 1,3-propanediol cyclo-sulfate (PCS), 1,3-propylene sultone (PS), 1,3-propylene sultone (PST) on the electrochemical performance of lithium nickel cobalt manganese oxide (NCM111)//graphite lithium-ion batteries were investigated herein. Some conclusions were obtained by comparing the results of the first charging-discharging efficiency, discharged capacity, rate characteristics, low-temperature discharging capability, high-temperature storage performance and cycle life, etc. C＝C double bond can improve the film-forming property and promote the cycle life, making VC possess a relatively balanced performance in all aspects and can be used independently. The continuous gas production for ES in the formation, cycle, and storage processes can be observed because of the unstoppable decomposition of the electrolyte, making it impossible to use. Sulphate Additives (DTD and PCS) can significantly reduce the DCR and improve the low-temperature performance; however, their high-temperature performance is slightly restricted. Sulfonate additives (PS and PST) have outstanding effects in inhibiting high-temperature flatulence. Especially, PST with dual functional groups has better cycle performance and capability to suppress the voltage decay in high-temperature environments than PS but has higher impedance in low-temperature environments than other additives. A comprehensive comparison shows that the single-component sulfur-containing additive is equipped with unique characteristics in some properties but also has obvious defects, making it lonely and impossible. The problem of poor cycling performance of sulfur-containing additives can be solved by proportionally compounding them with VC, while their characteristics such as high initial coulombic efficiency, low internal resistance, excellent rate performance and high-temperature stability can be maintained. The comprehensive performance of binary combination is better than that of the single-component additive, making it a better choice for additive combination to improve the battery performance.

Key words: electrolyte, additive, sulfur-containing, Li-ion, lithium nickel cobalt manganese oxide

CLC Number:

TM 911.3

Hengheng XIA, Pengcheng LIANG, Zhongxun AN. Effects of sulfur-containing electrolyte additives on the performance of lithium nickel cobalt manganese oxide//graphite Li-ion batteries[J]. Energy Storage Science and Technology, 2023, 12(8): 2390-2400.

Figures/Tables 6

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Table 1

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电解液添加剂	还原电位(vs. Li/Li⁺)/V	LUMO/eV	熔点/℃
碳酸亚乙烯酯(VC)	0.9 (1.0 mol/L LiPF₆-VC/DEC)^[21]	-0.01^[22]	22
亚硫酸乙烯酯(ES)	1.7 (1.0 mol/L LiPF₆-EC/DMC)^[4]	-1.25^[23]	-17
硫酸乙烯酯(DTD)	1.25 (1.0 mol/L LiPF₆-EC/DMC/EMC)^[24]	0.11^[24]	99
1,3-丙二醇环硫酸酯(PCS)	1.8 (1.0 mol/L LiPF₆-EC/DEC)^[25]	-0.34^[9]	60
1,3-丙烷磺酸内酯(PS)	0.74 (1.0 mol/L LiPF₆-EC/DMC)^[26]	0.03^[26]	30
1,3-丙烯磺酸内酯(PST)	1.12 (1.0 mol/L LiPF₆-EC/DMC)^[26]	-0.27^[26]	83

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