Bulk/Interfacial Synergetic Approaches Enable the Stable Anode for High Energy Density All-Solid-State Lithium–Sulfur Batteries

All-solid-state lithium–sulfur batteries (ASSLSBs) using solid-state electrolytes (SSEs) are believed to concurrently ensure high safety and decent electrochemical performance. However, the ASSLSBs still face several challenges on the anode side, including the interfacial incompatibility between Li/SSEs, dendritic problems, and dramatic volume expansion/contraction of Li metal during cycling. Herein, we propose bulk/interfacial synergetic approaches to overcome the above limitations by incorporating the Li-based lithium–boron (80LiB) alloy with a unique 3D skeleton and Ag@C modified layer. These synergistic approaches have proven to effectively alleviate the volume variation to retain the bulk electrode integrity, facilitate homogeneous Li dissolution/deposition to inhibit the formation of lithium dendrite, and suppress interfacial side reactions to maintain a stable interphase. Benefitting from our ingenious design, the ASSLSBs deliver a specific capacity of 1316 mAh g–1 and a capacity retention of 82% after 60 cycles. These approaches pave a new way to develop high energy density and high performance ASSLSBs.