Oxygen Vacancy Nanowires Regulate the Continuous Transport Pathways and Customized Ionic Microenvironment of Solid‐State Electrolytes for Stable Lithium Metal Batteries

Abstract Poly(vinylidene fluoride) (PVDF)‐based solid‐state electrolytes face critical challenges of sluggish ion transport and interfacial instability in lithium metal batteries, exacerbated by crystalline rigidity and residual organic solvents. Herein, a composite solid‐state electrolyte (M _3‐x PVH) integrating oxygen‐vacancy‐rich nanowires into a PVDF‐HFP matrix, which establishes the abundant continuous ion transport pathways and the customized ionic microenvironments, is designed. MoO _3‐x nanowires (SNWs) with abundant oxygen vacancies not only promote the flexibility of polymer chains and capture Li⁺ to form continuous ion transport pathways for obtaining high ion conductivity of 7.58×10 ⁻⁴ S cm ⁻¹ , but also selectively bind dimethylformamide to customize the ionic microenvironment for accelerating Li⁺ desolvation and enhancing interfacial stability. Importantly, oxygen‐vacancy‐rich nanowires repel anions via charge repulsion and favor anion decomposition, thus forming an inorganic‐rich SEI. Remarkably, Li metal anode achieves ultra‐long cycling (>8000 h at 0.1 mA cm ⁻² ) and demonstrates excellent performance paired with the high‐voltage cathode NCM811. This work pioneers a novel strategy for designing high‐performance solid‐state electrolytes by synergistically engineering material dimensionality and defect chemistry, unlocking new possibilities for next‐generation lithium‐metal batteries.