W-doping produced the two-phase (Fm3̄m and R3̄m) structure which improved the cycling and thermal stability of the Ni-rich layered cathodes.

Factors that determine the Li deposition behavior in Li-free ASSBs with a porous interlayer are systemically identified and Li deposition behavior is interpreted based on both thermodynamics and the kinetics.

Lithium metal, which exhibits the highest theoretical capacity and lowest redox potential relative to other materials, is considered to be the ultimate anode material for next-generation rechargeable batteries with energy...

Li‐free all‐solid‐state batteries can achieve high energy density and safety. However, separation of the current collector/solid electrolyte interface during Li deposition increases interfacial resistance, which deteriorates safety and reversibility. In this study, a reversible 3D porous anode is designed based on Li deposition behavior that depends on the pore size of the anode. More Li deposits are accommodated within the smaller pores of the Li hosting anode composed of Ni particles with a granular piling structure; this implies the Li movement into the anode is achieved via diffusional Coble creep. Surface modification of Ni with a carbon coating layer and Ag nanoparticles further increases the Li hosting capacity and enables Li deposition without anode/solid electrolyte interface separation. A Li‐free all‐solid‐state full cell with a LiNi0.8Mn0.1Co0.1O2 cathode shows an areal capacity of 2 mAh cm−2 for retaining a Coulombic efficiency of 99.46% for 100 cycles at 30 °C.

Despite the extensive interest in Li metal-based all-solid-state batteries (ASSBs) with sulfide solid electrolytes (SEs), the physically, chemically, and electrochemically unstable anodic interface has impeded the achievement of performance retention...