Model Studies on the Formation of the Solid Electrolyte Interphase: Reaction of Li with Ultrathin Adsorbed Ionic-Liquid Films and Co3O4(111) Thin Films

In this work we aim towards the molecular understanding of the solid electrolyte interphase (SEI) formation at the electrode electrolyte interface (EEI). Herein, we investigated the interaction between the battery-relevant ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI), Li and a Co₃O₄(111) thin film model anode grown on Ir(100) as a model study of the SEI formation in Li-ion batteries (LIBs). We employed mostly X-ray photoelectron spectroscopy (XPS) in combination with dispersion-corrected density functional theory calculations (DFT-D3). If the surface is pre-covered by BMP-TFSI species (model electrolyte), post-deposition of Li (Li⁺ ion shuttle) reveals thermodynamically favorable TFSI decomposition products such as LiCN, Li₂NSO₂CF₃, LiF, Li₂S, Li₂O₂, Li₂O, but also kinetic products like Li₂NCH₃C₄H₉ or LiNCH₃C₄H₉ of BMP. Simultaneously, Li adsorption and/or lithiation of Co₃O₄(111) to Li_nCo₃O₄ takes place due to insertion via step edges or defects; a partial transformation to CoO cannot be excluded. Formation of Co⁰ could not be observed in the experiment indicating that surface reaction products and inserted/adsorbed Li at the step edges may inhibit or slow down further Li diffusion into the bulk. This study provides detailed insights of the SEI formation at the EEI, which might be crucial for the improvement of future batteries.