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 Li1.2Ni0.13Co0.13Mn0.54O2 (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. Anode-free Li metal batteries integrating interface modification and surface prelithiation are designed for ultra-high energy densities. The interface is combined with a lithiophilic layer and a protective layer, which can regulate Li plating/stripping process, promote ion transportation, and prevent deactivation simultaneously. The surface prelithiated cathode can provide extra active Li ions for this zero-Li-excess system. image