Cathode-Electrolyte Interphase in a LiTFSI/Tetraglyme Electrolyte Promoting the Cyclability of V2O5.

V2O5, one of the earliest intercalation-type cathode materials investigated as a Li+ host, is characterized by an extremely high theoretical capacity (441 mAh g-1). However, the fast capacity fading upon cycling in conventional carbonate-based electrolytes is an unresolved issue. Herein, we show that using a LiTFSI/tetraglyme (1:1 in mole ratio) electrolyte yields a highly enhanced cycling ability of V2O5 (from 20% capacity retention to 80% after 100 cycles at 50 mA g-1 within 1.5-4.0 V vs Li+/Li). The improved performance mostly originates from the V2O5 electrode itself, since refreshing the electrolyte and the lithium electrode of the cycled cells does not help in restoring the V2O5 electrode capacity. Electrochemical impedance spectroscopy (EIS), post-mortem scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the origin of the improved electrochemical behavior. The results demonstrate that the enhanced cyclability is a consequence of a thinner but more stable cathode-electrolyte interphase (CEI) layer formed in LiTFSI/tetraglyme with respect to the one occurring in 1 M LiPF6 in EC/DMC (1:1 in weight ratio, LP30). These results show that the cyclability of V2O5 can be effectively improved by simple electrolyte engineering. At the same time, the uncovered mechanism further reveals the vital role of the CEI on the cyclability of V2O5, which can be helpful for the performance optimization of vanadium-oxide-based batteries.