Influence of Electrolyte Additives on the Degradation of Li2VO2F Li-Rich Cathodes

rich disordered rock-salt structures have, because of their high theoretical capacity, gained a lot of attention as a promising class of cathode materials for battery applications. However, the cycling stability of these materials has so far been less satisfactory. Here, we present three different film-forming electrolyte additives: lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), and glycolide, which all improve the cycling performance of the high-capacity Li-rich disordered rock-salt material Li2VO2F. The best performing additive, LiODFB, shows a 12.5% increase of capacity retention after 20 cycles. The improved cycling performance is explained by the formation of a protective cathode interphase on the electrode surface. Photoelectron spectroscopy is used to show that the surface layer is created from degradation of the electrolyte salt and additive cosalts. The cathode interphase can mitigate oxidation and following degradation of the active material, and thereby a higher degree of redox-active vanadium can be maintained after 20 cycles.