Cluster‐Directed Solvation Engineering for Dual‐Interface Stabilized Gel Polymer Electrolytes Enabling High‐Voltage and Fast‐Charging Lithium‐Ion Batteries

ABSTRACT Conventional LiPF 6 ‐based carbonate electrolytes undergo severe oxidative decomposition above 4.3 V, triggering uncontrolled interphase growth, transition‐metal dissolution, and accelerated capacity decay—challenges further compounded under fast‐charging and elevated‐temperature conditions. Herein, we propose a reactive‐cluster‐guided solvation reorganization strategy to reconstruct the Li + solvation structure and interfacial reaction pathways, thereby enabling dual‐interface stabilization. Highly polar MMDS spontaneously anchors PF 6 − via ion–dipole interactions, forming reactive (PF 6 − )–MMDS clusters, which redirect cathode‐side interfacial decomposition toward sulfur‐containing inorganic‐rich CEI formation, while LiDFOB reconstructs the primary Li + solvation sheath to enhance desolvation kinetics. Their coupled action yields thin, dense, and inorganic‐rich CEI/SEI layers, jointly suppressing parasitic reactions, transition‐metal dissolution, and rock‐salt surface reconstruction. With ultra‐low additive loading, LE‐HV@GPE delivers an ionic conductivity of 2.64 mS cm − 1 and a Li + transference number of 0.57. Gr‖NCM811 pouch cells achieve outstanding durability under high‐voltage (4.6 V), fast‐charging (3C), and elevated‐temperature (45°C) conditions, with full compatibility with existing manufacturing operations. This work establishes a solvation‐engineering paradigm for dual‐interface‐stabilized gel polymer electrolytes under harsh operating conditions.