Impact of Fluorine‐Based Lithium Salts on SEI for All‐Solid‐State PEO‐Based Lithium Metal Batteries

• Published in: Advanced functional materials 2023-09, Vol.33 (38)
• Main Authors: Li, Jiajia, Hu, Haiman, Fang, Wenhao, Ding, Junwei, Yuan, Du, Luo, Shuangjiang, Zhang, Haitao, Ji, Xiaoyan
• Format: Article
• Language: English
• Subjects: Electrolytes; Electrolytic cells; Energiteknik; Energy Engineering; Energy storage; Ethylene oxide; Fluorine; Lithium; Lithium batteries; Lithium fluoride; Materials science; Molten salt electrolytes; Polyethylene oxide; Solid electrolytes; Storage systems
• ISSN: 1616-301X; 1616-3028; 1616-3028
• DOI: 10.1002/adfm.202303718

LiF‐rich solid‐electrolyte‐interphase (SEI) can suppress the formation of lithium dendrites and promote the reversible operation of lithium metal batteries. Regulating the composition of naturally formed SEI is an effective strategy, while understanding the impact and role of fluorine (F)‐based Li‐salts on the SEI characteristics is unavailable. Herein, LiFSI, LiTFSI, and LiPFSI are selected to prepare solid polymer electrolytes (SPEs) with poly(ethylene oxide) and polyimide, investigating the effects of molecular size, F contents and chemical structures (F‐connecting bonds) of Li‐salts and revealing the formation of LiF in the SEI. It is shown that the F‐connecting bond is more significant than the molecular size and F element contents, and thus the performances of cells using LiPFSI are slightly better than LiTFSI and much better than LiFSI. The SPE containing LiPFSI can generate a high amount of LiF, and SPEs containing LiPFSI and LiTFSI can generate Li 3 N, while there is no Li 3 N production in the SEI for the SPE containing LiFSI. The preferential breakage bonds in LiPFSI are related to its position to Li anode, where Li‐metal as the anode is important in forming LiF, and consequently the LiPFSI reduction mechanism is proposed. This study will boost other energy storage systems beyond Li‐ion chemistries.