Cluster-Directed Solvation Engineering for Dual-Interface Stabilized Gel Polymer Electrolytes Enabling High-Voltage...

Conventional LiPF₆-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 PF₆ ^- via ion-dipole interactions, forming reactive (PF₆ ^-)-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.