Confinement‐Tailored High‐Concentration Electrolytes in Metal–Organic Frameworks for Durable Lithium‐Metal Batteries

Abstract High‐concentration electrolytes (HCEs) face inherent challenges such as high viscosity and diminished ionic conductivity caused by the formation of three‐dimensional (3D) anion networks, which limit their practical applications. In this study, it is demonstrated that encapsulating HCEs within metal–organic frameworks (MOFs) effectively disrupts these 3‐D networks, resulting in significantly enhanced ionic conductivity. Raman spectroscopy, nuclear magnetic resonance (NMR), and molecular dynamics (MD) simulations reveal a significant reduction in aggregates (AGGs)‐state anion within MOF‐confined electrolytes, confirming the reconstruction of the solvation environment. The MOF‐engineered electrolytes promote uniform lithium deposition and enable LiFePO 4 ||Li (LFP||Li) batteries to achieve stable cycling for over 400 cycles with minimal capacity decay. Remarkably, these batteries maintain stability at elevated temperatures and sustain the performance at 90 °C. By addressing the fundamental limitations of HCEs through nanoconfinement in MOFs, this work establishes an effective strategy for developing high‐performance and robust energy storage systems.