Rational Design of Ion Transport Paths at the Interface of Metal-Organic Framework Modified Solid Electrolyte

Solid-state lithium batteries have attracted great attention owing to their potential advantages in safety and energy density. Among various solid electrolytes, solid polymer electrolyte is promising due to its good viscoelasticity, lightweight, and low-cost processing. However, key issues of solid polymer electrolyte include poor ionic conductivity and low Li⁺ transference number, which limit its practical application. Herein, a new-type of ultraviolet cross-linked composite solid electrolyte (C-CSE), composed of ZIF-based ionic conductor (named ZIL) and polymer, is designed with enhanced ion transport. The ZIL is composed of ZIF-8 and ionic liquid, which can provide C-CSE with fast ion transport paths. Moreover, the proper pore size of ZIF-8 can restrict the migration of embedded ionic liquid and thus construct a solid-liquid transport interface between polymer chains and ZIF-8, which could achieve fast ion transport. In addition, ultraviolet irradiation can decrease the crystallization of C-CSE and thus increase the amorphous region. Consequently, the C-CSE show excellent electrochemical performance including high ionic conductivity of 0.426 mS cm^-1 at 30 °C, high Li⁺ transference number of 0.67, and good Li|Li compatibility cycle over 1040 h. Experimental and computational results indicate that diffusion energy barrier of Li⁺ through ZIF-8 is smaller than that of polymer chains, which reveals a new Li⁺ transport mechanism between polymer chains and ZIL, from "chain-chain-chain" to "chain-ZIL-chain". This work demonstrates rational design of ion transport paths at the interface of solid electrolyte could facilitate the development of solid-state lithium batteries as a promising novel strategy.