Impact of Glyme Ether Chain Length on the Interphasial Stability of Lithium‐Electrode in High‐Capacity Lithium‐Metal Battery

Abstract The realization of lithium‐metal (Li) batteries faces challenges due to dendritic Li deposition causing internal short‐circuit and low Coulombic efficiency. In this regard, the Li‐deposition stability largely depends on the electrolyte, which reacts with Li to form a solid electrolyte interphase (SEI) with diverse physico‐chemical properties, and dictates the interphasial kinetics. Therefore, optimizing the electrolyte for stability and performance remains pivotal. Hereof, glyme ethers are an emerging class of electrolytes, showing improved compatibility with metallic Li and enhanced stability in Li─Air and Li─Sulfur batteries. Yet, the criteria for selecting glyme solvents, particularly concerning Li deposition and dissolution processes, remain unclear. The SEI characteristics and Li deposition/dissolution processes are investigated in glyme‐ether‐based electrolytes with varying chain lengths, using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO₃) salts under high capacity and limited electrolyte conditions. Longer glymes led to more homogeneous SEI, particularly pronounced with LiNO₃, minimizing surface roughness during stripping, and promoting compact Li deposits. Higher reductive stability, resulting in homogeneous interphasial properties, and slower kinetics due to high desolvation barrier and viscosity, underline stable Li growth in longer glymes. This study clarifies factors guiding the selection of glyme ether‐based electrolytes in Li metal batteries, offering insights for next‐generation energy storage systems.