The carrier alternation from Li atoms to Li vacancies leads to interface instability in solid-state lithium alloy anodes.
The stable cycling of energy-dense solid-state batteries is highly relied on the kinetically stable solid-state Li alloying reactions. The Li metal precipitation at solid-solid interfaces is the primary cause of interface fluctuations and battery failures, whose formation requires a clear mechanism interpretation, especially on the key kinetic short board. Here, we introduce the lithium alloy anode as a model system to quantify the Li kinetic evolution and transition from the alloying reaction to the metal deposition in solid-state batteries, identifying that there is a carrier transition from Li atoms to Li vacancies during lithiation processes. The rate-determining step is charge transfer or Li atom diffusion at different lithiation stages.