Highly Ionic Conductive, Self-Healing, Li₁₀GeP₂S₁₂-Filled Composite Solid Electrolytes Based on Reversibly Interlocked Macromolecule Networks for Lithium Metal Batteries with Improved Cycling Stability

Abstract

Ceramic−polymer composite solid electrolytes (CSEs) have attracted great attention by combining the advantages of polymer electrolytes and inorganic ceramic electrolytes. Herein, Li 10 GeP 2 S 12 (LGPS) particles are incorporated into poly(ethylene oxide) (PEO)-based reversibly interlocked polymer networks (RILNs) derived from the topological rearrangement of two PEO networks cross-linked by reversible imine bonds and disulfide linkages. A series of highly ionic conductive, self-healing CSEs are obtained accordingly. The interlocking architecture successfully inhibits PEO crystallization, increasing the amorphous phase for Li ion transportation, and stabilizes the conductive pathways of LGPS particles by its unique confinement effect. Meanwhile, the LGPS particles cooperate with the RILN matrix, forming a filler−polymer interfacial phase for additional Li ion transportation and strengthening and toughening the resultant CSEs via the strong intermolecular Li + −O 2− interactions. Furthermore, the dynamic characteristics of the included reversible bonds ensure a multiple intrinsic self-healing capability. Consequently, the CSEs containing 15 wt % LGPS deliver a high ionic conductivity (1.06 × 10 −3 S cm −1 ) and high Li ion transference number (∼0.6) at 25 °C, a wide electrochemical stability window (>4.9 V), good mechanical properties (0.63 MPa, 377%), and a stable CSE/Li anode interface. The integrated Li/CSE/LiFePO 4 battery exhibits a specific discharge capacity of 110.8 mAh g −1 at 1 C (25 °C) and a capacity retention of 76.9% after 200 cycles. Thanks to the healability, the damaged CSEs can regain the structural integrity, ion conductive capability, and cycling performance of the assembled cells. The present work provides an effective strategy to fabricate CSEs for lithium metal batteries that are workable at ambient temperature.