LAUSR

Although solid composite electrolytes show tremendous potential for the practical solid‐state lithium metal batteries, searching for a straightforward tactic to promote the ion conduction at electrolyte/electrode interface, especially settling lithium dendrites formation caused by the concentration gradient polarization, are still long‐standing problems. Here, the authors report a corrugated 3D nanowires‐bulk ceramic‐nanowires (NCN) skeleton reinforced composite electrolyte with regulated interfacial Li‐ion transport behavior. The special and integrated NCN skeleton endows the electrolyte with fast Li‐ion transfer and solves the Li+ concentration polarization at electrode/electrolyte interface, thereby eliminating the energy barrier originated from the redistribution of charge carriers and offering homogeneous interfacial Li‐ion flux on lithium anode. As a “double insurance”, the bulk ceramic sheet in 3D framework enables the electrolyte to block the mobility of anions. The rational designed NCN composite electrolyte exhibits excellent ionic conductivity and the assembled all‐solid‐state battery possesses 90.2% capacity retention after 500 cycles. The proposed strategy affords a special insight in designing high‐performance solid composite electrolytes.