Biomimetic Channels Design in Metal‐Organic Framework Enabling Highly Lithium‐Ion Conduction for Lithium‐Metal Batteries

Abstract Solid‐state electrolytes (SSEs) based on metal‐organic frameworks (MOFs) are an ideal material for constructing high‐performance lithium metal batteries (LMBs). However, the low ion conductivity and poor interface contact (especially at low temperatures) still seriously hinder its further application. Herein, inspired by the Na + /K + conduction in biology systems, a series (NH 2 , OH, NH‐(CH 2 ) 3 ‐SO 3 H)‐modified MIL‐53‐X as SSEs is reported. These functional groups are similar to anions suspended in biological ion channels, partially repelling anions while allowing cations to be effectively transported through pore channels. Subsequently, MIL‐53‐X with hierarchical pore structure (H‐MIL‐53‐X) is obtained by introducing lauric acid as a regulator, and then the effects of structural design and morphology control on its performance are explored. The conductivity of H‐MIL‐53‐NH‐SO 3 Li with multi‐level pore structure and modified by sulfonic acid groups reached 2.2 × 10 −3 S cm −1 at 25 °C, lithium‐ion transference number of 0.78. Besides, the H‐MIL‐53‐NH‐SO 3 Li still has an excellent conductivity of 10 −4 S cm −1 at −40 °C. Additionally, LiFePO 4 /Li batteries equipped with H‐MIL‐53‐NH‐SO 3 Li SSEs could operate stably for over 200 cycles at 0.1 C. The strategy of combining structural and morphological design of MOFs with biomimetic ion channels opens new avenues for the design of high‐performance SSEs.