锂离子电池电解液中新型氟化物的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0401

摘要/Abstract

摘要：

随着便携式电子设备和电动汽车的快速发展，对具有高能量密度和安全性的锂离子电池提出了迫切需求。开发具有宽电化学窗口和不易燃的电解液对于实现锂离子电池的高能量密度和安全性至关重要。然而，常规碳酸酯电解液存在电化学窗口较窄和易燃烧的问题，限制了其发展。在电解液中引入含氟化合物可以改善电解液的成膜性、氧化稳定性和燃烧性并可有效地提升电池的综合性能。本文从锂盐和溶剂两个方面综述了新型氟化物在锂离子电池电解液中的研究进展，首先介绍了三种新型含氟锂盐在热稳定性、电化学稳定性、成膜性以及对铝集流体的钝化能力等方面的特性，其次比较了碳酸酯、羧酸酯、醚、芳香烃等溶剂氟取代前后的物理化学性质，以及对电解液的离子电导率、界面形成能力、抗氧化性、宽温性能和易燃性等方面的影响，重点介绍了部分新型氟代碳酸酯、氟代醚及氟代芳香烃溶剂在锂离子电池电解液中的应用，最后总结了氟化物开发和应用中的科学挑战和局限性，并展望了其在锂离子电池电解液中的未来发展方向。

关键词: 锂离子电池, 电解液, 锂盐, 有机溶剂, 含氟化合物

Abstract:

The proliferation of portable electronic devices and electric vehicles has led to the pressing need for lithium-ion batteries (LIBs) with enhanced energy density and safety. The utilization of wide-electrochemical window electrolytes with non-combustible properties is crucial in achieving the desired battery characteristics. However, conventional carbonate electrolytes suffer from a narrow electrochemical window and easy combustion, consequently limiting the development of high-energy density and -safety batteries. Incorporating fluorinated compounds into electrolytes can improve the film formation, oxidation stability, and combustibility of electrolytes and effectively enhance the overall battery performance. This review paper provides an overview of the recent advancements in the utilization of new fluorinated compounds as lithium salts and solvents in LIB electrolytes. First, the properties of three new fluorinated lithium salts are presented in terms of thermal and electrochemical stabilities, film formation, and passivation ability for aluminum collectors. Next, the physicochemical properties of carbonate, carboxylic acid esters, ethers, aromatic hydrocarbons, and other solvents before and after fluoridation are compared along with the improvements in the ionic conductivity, interfacial formation ability, oxidation resistance, wide temperature performance, and flammability of electrolytes. Focusing on the application of some new fluorocarbonates, fluorinated ethers, and fluorinated aromatic hydrocarbon solvents to LIB electrolytes, we then finally summarize the scientific challenges and the limitations associated with the development and application of fluorine-containing compounds, providing an outlook on their future prospects in LIB electrolyte systems.

Key words: lithium-ion battery, electrolyte, lithium salt, organic solvent, fluorinated compound

中图分类号:

TM 912.9

汪心兰, 曾子琪, 张涵, 雷盛, 谢佳. 锂离子电池电解液中新型氟化物的研究进展[J]. 储能科学与技术, 2023, 12(10): 3075-3086.

Xinlan WANG, Ziqi ZENG, Han ZHANG, Sheng LEI, Jia XIE. Research progress of new fluorinated compounds in lithium-ion battery electrolytes[J]. Energy Storage Science and Technology, 2023, 12(10): 3075-3086.

图/表 5

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溶剂	熔点T_m/℃	沸点T_b/℃	密度 ρ (25 ℃)/(g/cm³)	相对介电常数 ε_r (20 ℃)	黏度 η (20℃)/(×10^-3 Pa·s)
碳酸乙烯酯	37.5	238	1.321	90.5(40 ℃)	1.94(40 ℃)
氟代碳酸乙烯酯	20	210	1.48	79.7	4.4/2.3(40 ℃)
双氟代碳酸乙烯酯	8.5	129	1.52	35.4	2.7
三氟代碳酸乙烯酯	-54.5	91	1.6	18	1.28
碳酸二乙酯	-75	126	0.975	2.8	0.82
氟代碳酸二乙酯	—	135	1.06	7.5	1.21
四氟代碳酸二乙酯	-28.5	127.5	1.18	8.3	1.87

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