锂离子电池硅基负极电解液成膜添加剂的研究进展

doi:10.11949/0438-1157.20221106

摘要/Abstract

摘要：

锂离子电池是能源储存和利用的一项关键技术，能量密度已成为现代电池发展中的一个关键指标。硅基负极由于其较高的理论比容量，得到广泛关注，但硅基材料存在严重的体积膨胀问题。功能性添加剂对电池性能有明显的改善效果，是电解液体系不可缺少的部分，具有“用量小，见效快”的特点，通过成膜添加剂形成稳定的固态电解质界面（SEI）膜进而稳定电极电解液界面，改善硅基负极电池性能。本文总结了近年来硅基负极电解液成膜添加剂的研究进展，对成膜添加剂按照官能团或元素进行分类论述，并对多组分成膜添加剂的协同作用进行了简要阐述。最后，针对目前硅基负极电解液添加剂的研究现状进行了总结，并展望了未来的研究方向。

关键词: 电化学, 电解质, 界面, 锂离子电池, 硅基负极, 成膜添加剂, 协同作用

Abstract:

Lithium-ion batteries are a key technology for energy storage and utilization. Energy density has become a key indicator in the development of modern batteries. Si-based anodes have received extensive research attention due to their high theoretical specific capacity. But the Si-based materials suffer from serious volume expansion problems. Functional additives are an indispensable part of the electrolyte system which has a significant improvement effect on battery performance, with the characteristics of “small dosage, quick effect”. A stable solid-state electrolyte interface (SEI) film is formed by film-forming additives to stabilize the electrode-electrolyte interface and improve the performance of Si-based anode batteries. This paper summarizes the research progress on film-forming additives for Si-based anodes in recent years. The film-forming additives are discussed in categories according to functional groups or elements, and the synergistic effect of multi-component film-forming additives is briefly described. Finally, the current research status of electrolyte additives for Si-based anodes is summarized and future research directions are prospected.

Key words: electrochemistry, electrolyte, interface, lithium-ion battery, Si-based anode, film-forming additive, synergistic effect

中图分类号:

TM 911

程伟江, 汪何琦, 高翔, 李娜, 马赛男. 锂离子电池硅基负极电解液成膜添加剂的研究进展[J]. 化工学报, 2023, 74(2): 571-584.

Weijiang CHENG, Heqi WANG, Xiang GAO, Na LI, Sainan MA. Research progress on film-forming electrolyte additives for Si-based lithium-ion batteries[J]. CIESC Journal, 2023, 74(2): 571-584.

图/表 17

图1 LiPO2F2在硅负极表面的成膜机理[22]

Fig.1 Film formation mechanism of LiPO2F2 on silicon anode[22]

图2 锂盐添加剂的分子结构

Fig.2 Molecular structure of lithium salt additives

图3 溶剂衍生添加剂的分子结构

Fig.3 Molecular structure of solvent derivative additives

图4 EC和lacOCA在硅负极形成SEI膜的示意图[29]

Fig.4 Schematic illustration of the SEI formation with EC and lacOCA on silicon anode[29]

图5 含氟添加剂分子结构

Fig.5 Molecular structure of fluorine-containing additives

图6 FEC还原反应途径示意图[32]

Fig.6 Schematic illustration of FEC reduction reaction[32]

图7 TFPC调控SEI膜结构和组成示意图[35]

Fig.7 Schematic illustration of TFPC in regulating the structure and composition of the SEI[35]

图8 含氮添加剂分子结构

Fig.8 Molecular structure of nitrogen-containing additives

图9 N-CAs开环反应机制[43]

Fig.9 Mechanism of a reductive ring-opening reaction of N-CAs[43]

图10 含硫添加剂分子结构

Fig.10 Molecular structure of sulfur-containing additives

图11 TEOS作用下硅氧烷网络的形成机理[44]

Fig.11 Mechanism of a siloxane network formation under TEOS[44]

图12 硅烷添加剂分子结构

Fig.12 Molecular structure of organosilicon additives

图13 离子液体添加剂分子结构

Fig.13 Molecular structure of ionic liquid additives

图14 充放电过程Li-M-Si三元化合物形成示意图[57]

Fig.14 Schematic illustration of Li-M-Si ternary phases formation during the charging and discharging[57]

图15 其他添加剂分子结构

Fig.15 Molecular structure of other additives

图16 协同作用添加剂分子结构

Fig.16 Molecular structure of additives with synergistic effect

图17 DMVC-OCF3、DMVC-OTMS和VC构建稳定界面层示意图[69]

Fig.17 Schematic illustration of DMVC-OCF3, DMVC-OTMS and VC for building stable SEI[69]

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