Anion-Dependent Potential Precycling Effects on Lithium Deposition/Dissolution Reaction Studied by an Electrochemical Quartz Crystal Microbalance

The electrochemical quartz crystal microbalance technique was employed to study the initial stage of the electrodeposition and dissolution of lithium utilizing three kinds of electrolyte solutions such as LiPF₆, LiTFSI, or LiFSI in tetraglyme. The native-SEI (solid–electrolyte interphase) formed by a potential prescan before lithium deposition/dissolution in all three solutions. Simultaneous additional SEI (add-SEI) deposition and its dissolution with lithium deposition and dissolution, respectively, were observed in LiPF₆ and LiTFSI. Conversely, the add-SEI dissolution with lithium deposition and its deposition with lithium dissolution were observed in LiFSI. Additional potential precycling resulted in the accumulation of a “pre-SEI” layer over the native-SEI layer in all of the solutions. With the pre-SEI, only lithium deposition/dissolution were significantly observed in LiTFSI and LiFSI. On the basis of the potential dependences of the mass and resistance changes, the anion-dependent effects of such a pre-SEI layer presence/absence on the lithium deposition/dissolution processes were discussed.