Constructing Ion Bridges With Competitive Coordination Effects to Promote Li ⁺ Conduction in Solid‐State Electrolytes for High‐Performance Lithium Metal Batteries

ABSTRACT Composite solid electrolytes (CSEs) based on poly(vinylidene fluoride)‐co‐hexafluoropropylene (PVDF‐HFP) and Li _6.4 La ₃ Zr _1.4 Ta _0.6 O ₁₂ (LLZTO) are considered among the most promising SEs for achieving high‐energy‐density solid‐state batteries. However, low ionic conductivity and poor interfacial compatibility pose significant challenges for their practical applications. Herein, a strategy involving the construction of Li _x TaO _x F _{5‐ x} (LTOF) ion bridges with competitive coordination effects on the LLZTO surface is proposed. This approach alleviates restrictions on Li ⁺ transport and enhances Li ⁺ transport kinetics. The introduction of LTOF weakens Li ⁺ coordination strength, suppresses electron localization at the LLZTO/PVDF‐HFP interface, and simultaneously reduces PVDF‐HFP crystallinity. This creates multiple efficient Li ⁺ transport pathways and an interphase with excellent compatibility. Consequently, the prepared electrolyte exhibits a high ionic conductivity of 1.21 mS cm ^{− 1} . Attributing to easier lithium salt dissociation, the solid electrolyte interface enriched with inorganic components, e.g. LiF/Li ₃ N/Li ₂ S, enables the Li|CSE‐9TF|Li cell to maintain stable plating/stripping for over 1100 h at a current density of 0.8 mA cm ^{− 2} . The assembled LiFePO ₄ ||Li cells deliver high capacity retention (93.4%) and approaching 100% coulombic efficiency after 1000 cycles at 1C. This work proposes a strategy for regulating the coordination environment and improving interfacial compatibility through surface oxyhalide layers, facilitating new progress in the practical application of CSEs.