Stabilizing Lithium Plating by a Biphasic Surface Layer Formed In Situ

The dendritic growth of Li metal leads to electrode degradation and safety concerns, impeding its application in building high energy density batteries. Forming a protective layer on the Li surface that is electron‐insulating, ion‐conducting, and maintains an intimate interface is critical. We herein demonstrate that Li plating is stabilized by a biphasic surface layer composed of a lithium‐indium alloy and a lithium halide, formed in situ by the reaction of an electrolyte additive with Li metal. This stabilization is attributed to the fast lithium migration though the alloy bulk and lithium halide surface, which is enabled by the electric field across the layer that is established owing to the electron‐insulating halide phase. A greatly stabilized Li‐electrolyte interface and dendrite‐free plating over 400 hours in Li|Li symmetric cells using an alkyl carbonate electrolyte is demonstrated. High energy efficiency operation of the Li₄Ti₅O₁₂ (LTO)|Li cell over 1000 cycles is achieved.