高镍锂离子电池三元材料NCM电解质的应用

doi:10.16085/j.issn.1000-6613.2020-0973

摘要/Abstract

摘要：

高镍三元正极材料成本低、比容量高，符合锂离子电池可持续发展的理念，被认为是下一代的主流正极材料。但是，高镍材料需搭配合适的电解质才能有效发挥其性能，而这一研究很少被关注。因此，总结并选择适配的电解质对于高镍锂离子电池来说格外重要。本文简述了锂离子电池电解质的一般组成及其产生的电解质类型，重点综述了有机液体电解质、固体电解质及离子液体基电解质在高镍三元材料电池中的应用，并通过电解质的量化计算进行了验证总结。分析表明，离子液体-有机溶剂混合电解质在高镍三元材料（NCM）电池中具备更好的循环效果，同时满足了电池安全稳定的要求，更适合作为高镍材料电池的电解质。最后，针对混合电解质各溶剂间的相互作用机理及Li⁺传输等分子动力学研究进行了展望。

关键词: 高镍三元正极材料, 锂离子电池, 电解质, 离子液体, 量化计算

Abstract:

Nickel-rich ternary cathode materials have low cost and high specific capacity, which are suitable for the sustainable development of lithium-ion batteries and have been considered as the mainstream of next-generation cathode material. However, nickel-rich materials need to used together with suitable electrolytes to effectively give their best performance, which is however paid little attention. Selecting suitable electrolytes is particularly important for nickel-rich lithium-ion batteries. This paper briefly described the general types and composition of the electrolytes for lithium-ion battery. Next, we focused on the application of organic electrolytes, solid electrolytes and ionic liquid-based electrolytes in nickel-rich ternary material batteries, which were assessed through quantitative calculations. The results showed that the ionic liquid-organic solvent hybrid electrolyte presented very good circulation performance in nickel-rich NCM batteries, while meeting the requirements of the battery on safety and stability, and therefore was more suitable for nickel-rich NCM battery. Finally, the molecular dynamics studies on the interaction mechanism and Li⁺ transport between different solvents of hybrid electrolyte were prospected.

Key words: nickel-rich ternary cathode material, lithium-ion battery, electrolytes, ionic liquids-based, quantitative calculation

中图分类号:

TQ150.1

张文林, 刘雪娇, 马青查, 杨双丞, 张永康, 李春利. 高镍锂离子电池三元材料NCM电解质的应用[J]. 化工进展, 2021, 40(4): 2175-2187.

ZHANG Wenlin, LIU Xuejiao, MA Qingcha, YANG Shuangcheng, ZHANG Yongkang, LI Chunli. Application of NCM electrolyte for nickel-rich lithium ion battery[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2175-2187.

图/表 21

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类别	优势	弊端
有机液体电解质（含添加剂）	成本低，流动性好，电导率高，电极成膜性好，在NCM电池中具有较高的放电比容量	易燃，安全性低
固体电解质	具有较高的机械稳定性，安全不易燃，能有效稳定NCM电极结构	离子电导率低，电化学窗口较低，不利于高压NCM材料电池循环
纯离子液体电解质	电化学稳定性和热稳定性好，不易燃，电化学窗口宽，离子电导率较高	黏度大，与NCM电极润湿性差，循环能力弱，ILs成本高
离子液体-有机溶剂混合电解质	安全稳定性较高，黏度较低，与NCM电极相容性好，循环性高	ILs成本高

类别	优势	弊端
有机液体电解质（含添加剂）	成本低，流动性好，电导率高，电极成膜性好，在NCM电池中具有较高的放电比容量	易燃，安全性低
固体电解质	具有较高的机械稳定性，安全不易燃，能有效稳定NCM电极结构	离子电导率低，电化学窗口较低，不利于高压NCM材料电池循环
纯离子液体电解质	电化学稳定性和热稳定性好，不易燃，电化学窗口宽，离子电导率较高	黏度大，与NCM电极润湿性差，循环能力弱，ILs成本高
离子液体-有机溶剂混合电解质	安全稳定性较高，黏度较低，与NCM电极相容性好，循环性高	ILs成本高

类别	电导率 /mS·cm^-1	电化学窗口（vs.Li/Li⁺） /V	首次充放电循环（0.1C） /mA·h·g^-1	界面阻抗（100圈循环后） /Ω
有机液体电解质（含添加剂）	9.3	5.0	186.8	58.3
固体电解质	0.6	3.2	144.3	37.6
纯离子液体电解质	1.4	7.0	146.6	38.2
离子液体-有机溶剂混合电解质	9.8	5.6	190.6	32.9

类别	电导率 /mS·cm^-1	电化学窗口（vs.Li/Li⁺） /V	首次充放电循环（0.1C） /mA·h·g^-1	界面阻抗（100圈循环后） /Ω
有机液体电解质（含添加剂）	9.3	5.0	186.8	58.3
固体电解质	0.6	3.2	144.3	37.6
纯离子液体电解质	1.4	7.0	146.6	38.2
离子液体-有机溶剂混合电解质	9.8	5.6	190.6	32.9

分子名称	HOMO/eV	LOMO/eV
EC	-8.468	-0.604
DEC	-8.055	-0.268
DMC	-8.179	-0.370
EMC	-8.133	-0.256