Li-ion solvation in TFSI and FSI -based ionic liquid electrolytes probed by X-ray photoelectron spectroscopy

Abstract

For Li-ion batteries, the Li-ion solvation in liquid electrolytes is a crucial parameter affecting directly the electrochemical cycling performance. X-ray photoelectron spectroscopy (XPS) can play an essential role for investigating the cation and anion electronic structure and monitoring the Li-ion solvation into various solvent and salt environments. In this contribution, we demonstrate the capability of conventional laboratory XPS using Al Kα X-ray source to determine the anions solvation shell of Li+ cation within the low vapour pressure and vacuum compatible ionic liquid electrolytes. 1M of LiTFSI and 1M of LiFSI salts dissolved in (EMIM+-FSI-) and (EMIM+-TFSI-) ionic liquids respectively are investigated by acquiring the F1s, N1s, C1s, S2p and Li1s core levels. The binding energy difference between the N1s component originating from the EMIM+ cation and the N1s component originating from TFSI- or FSIanions solvating the Li+ confirms that both TFSI- and FSIcontribute simultaneously to the Li+ solvation. Additionally, the stability of the TFSI and FSI -based ionic liquid electrolytes is carefully discussed for long X-ray exposure times.