Artificial Crystalline‐Amorphous Architecture Enables Continuous Ion Transport in Poly(Vinylidene Fluoride)‐Based Solid‐State Electrolytes

ABSTRACT Solid‐state polymer electrolytes (SPEs) hold promises for next‐generation batteries but are hindered by low ionic conductivities. This issue stems from crystalline regions that block long‐range ion transport in amorphous phases, while fully amorphous polymers are mechanically unstable. Here we design an “artificial crystalline‐amorphous” architecture that converts the isolated amorphous conduction zones into continuous, long‐range pathways. This is achieved by infiltrating a fully amorphous poly (vinylidene fluoride‑co‑chlorotrifluoroethylene) (PVT) into an oriented electrospun fibrous framework of polar semi‑crystalline PVT. The framework serves as an “artificial crystalline phase,” offering robust mechanical support and facilitating lithium‑salt dissociation. Simultaneously, the amorphous phase utilizes this microscale network to enable long‐range ion conduction. The resulting SPEs exhibit an extremely high ionic conductivity of 1.23 mS cm ⁻¹ at 25°C, outperforming most reported all‐polymeric‐SPEs (10 ⁻⁷ ∼ 10 ⁻⁵ S/cm). Li//Li symmetric cells demonstrate stable cycling over 1300 h at 0.2 mA cm ⁻² , in clear contrast to 60 h for the controlled cell. Furthermore, assembled high‐voltage Ni _0.8 Co _0.1 Mn _0.1 O ₂ (NCM811)//Li full cells also deliver a stable cycling performance at 25°C. This work opens a new route for improving ion transport efficiency by constructing an artificial crystalline‐amorphous structure.