Heterogeneous Nanodomain Electrolytes for Ultra‐Long‐Life All‐Solid‐State Lithium‐Metal Batteries

Solid polymer electrolytes exhibit huge advantages but are hindered by insufficient mechanical strength and ionic conductivity in the applications of all‐solid‐state lithium‐metal batteries (ASSLBs). Herein, poly(ether‐block‐amide) (Pebax) strategies to construct heterogeneous nanodomain electrolytes (HNEs) for ultra‐long‐life ASSLBs are introduced. Pebax HNEs forms conductive nanodomains via phase separation, exhibiting interconnected and high Li + conductive features. Compared with conventional PEO‐based electrolytes, the Pebax HNEs with controllable size and order can facilitate rapid Li + transport with steerable transport channels, further enhancing the Li + conductivity and inducing the uniform Li + deposition. Furthermore, the obtained thin and dense hybrid SEI layer with potent mechanical strength can synergistically suppress the dendrite growth, and the as‐prepared ASSLBs exhibit a satisfactory capacity with a tiny capacity reduction of 0.013% per cycle over 1500 cycles. This work provides a brand‐new insight to construct a conductive structure in electrolytes for high‐performance ASSLBs.