High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes

Silicon anodes are regarded as one of the most promising alternatives to graphite for high energy‐density lithium‐ion batteries (LIBs), but their practical applications have been hindered by high volume change, limited cycle life, and safety concerns. In this work, nonflammable localized high‐concentration electrolytes (LHCEs) are developed for Si‐based anodes. The LHCEs enable the Si anodes with significantly enhanced electrochemical performances comparing to conventional carbonate electrolytes with a high content of fluoroethylene carbonate (FEC). The LHCE with only 1.2 wt% FEC can further improve the long‐term cycling stability of Si‐based anodes. When coupled with a LiNi0.3Mn0.3Co0.3O2 cathode, the full cells using this nonflammable LHCE can maintain >90% capacity after 600 cycles at C/2 rate, demonstrating excellent rate capability and cycling stability at elevated temperatures and high loadings. This work casts new insights in electrolyte development from the perspective of in situ Si/electrolyte interphase protection for high energy‐density LIBs with Si anodes. A nonflammable localized high‐concentration electrolyte (LHCE) with a small amount of fluoroethylene carbonate significantly enhances the performances of silicon anodes. The concept of forming locally highly‐coordinated lithium ion‐solvent solvates and a robust salt‐derived “lithium fluoride‐rich” solid electrolyte interphase on Si anodes from the LHCE offers a promising avenue to overcome the challenges of Si anodes in lithium ion batteries.