Beyond the Hype: Decoding Bis(fluorosulfonyl)imide Chemistry in Advanced Lithium‐Sulfur Batteries

Lithium-sulfur batteries (LSBs) are one of the most promising candidates for next-generation energy storage due to their high theoretical energy density and cost-effective active material. However, challenges such as polysulfide shuttling and lithium metal instability hinder their practical deployment. To tackle these challenges, in this study, we delve into the critical impacts of salt anion in the electrochemical performance of LSBs, focusing on a family of localized high-concentration electrolytes (LHCEs) comprising two prevalent anions [i.e., lithium bis(fluorosulfonyl)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)]. While higher LiFSI content enhances ionic conductivity, SEI formation, and lithium metal compatibility, it also reduces sulfur utilization due to side reactions with long-chain polysulfides. Post-mortem analyses confirm the formation of insulating species in high-LiFSI formulations. An optimal electrolyte composition with 0.2 m LiFSI as co-salt offers excellent electrochemical performance, achieving enhanced lithium protection and stabilized sulfur redox reactions. These findings reveal the coordination-dependent, double-edged nature of LiFSI and provide key insights for electrolyte design in high-performance LSBs.