Toward High‐Energy‐Density Initial‐Anode‐Free Lithium‐Metal Batteries via Ultra‐Thin Protective Ion‐Transport‐Promoting Interface Modification and Surface Prelithiation

Anode-free lithium-metal batteries (AFLMBs) are desirable candidates for achieving high-energy-density batteries, while severe active Li⁺ loss and uneven Li plating/stripping behavior impede their practical application. Herein, a trilaminar LS-Cu (LiCPON + Si/C-Cu) current collector is fabricated by radio frequency magnetron sputtering, including a Si/C hybrid lithiophilic layer and a supernatant carbon-incorporated lithium phosphorus oxynitride (LiCPON) solid-state electrolyte layer. Joint experimental and computational characterizations and simulations reveal that the LiCPON solid-state electrolyte layer can decompose into an in situ stout ion-transport-promoting protective layer, which can not only regulate homogeneous Li plating/stripping behavior but also inhibit the pulverization and deactivation of Si/C hybrid lithiophilic layer. When combined with surface prelithiated Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (Preli-LRM) cathode, the Preli-LRM||LS-Cu full cell delivers 896.1 Wh kg^-1 initially and retains 354.1 Wh kg^-1 after 50 cycles. This strategy offers an innovative design of compensating for active Li⁺ loss and inducing uniform Li plating/stripping behavior simultaneously for the development of AFLMBs.