Tuning the Formation and Structure of the Silicon Electrode/Ionic Liquid Electrolyte Interphase in Superconcentrated Ionic Liquids

The latest advances in the stabilization of Li/Na metal battery and Li-ion battery cycling have highlighted the importance of electrode/electrolyte interface [solid electrolyte interphase (SEI)] and its direct link to cycling behavior. To understand the structure and properties of the SEI, we used combined experimental and computational studies to unveil how the ionic liquid (IL) cation nature and salt concentration impact the silicon/IL electrolyte interfacial structure and the formed SEI. The nature of the IL cation is found to be important to control the electrolyte reductive decomposition that influences the SEI composition and properties and the reversibility of the Li–Si alloying process. Also, increasing the Li salt concentration changes the interface structure for a favorable and less resistive SEI. The most promising interface for the Si-based battery was found to be in P1222FSI with 3.2 m LiFSI, which leads to an optimal SEI after 100 cycles in which LiF and trapped LiFSI are the only distinguishable lithiated and fluorinated products detected. This study shows a clear link between the nanostructure of the IL electrolyte near the electrode surface, the resulting SEI, and the Si negative electrode cycling performance. More importantly, this work will aid the rational design of Si-based Li-ion batteries using IL electrolytes in an area that has so far been neglected, reinforcing the benefits of superconcentrated electrolyte systems.