Yb ₂ O ₃ ‐Polyoxometalate Sub‐1 nm Heterogeneous Cluster Chains with Local Electron Rearrangement for Accelerated Li ⁺ Transport in Composite Solid Electrolytes

Composite solid-state electrolytes have received widespread attention due to their excellent comprehensive performance. Herein, sub-1 nm Yb₂O₃-based polyoxometalates heterogeneous cluster chains (YOP) are designed to construct enrich and continuous Li⁺ interface pathways. The terminal oxygen in phosphomolybdic acid attracts local electrons from Yb in the heterogeneous structure, inducing electron rearrangement and strengthening the local positive charge of Yb³⁺, which enhances interfacial interactions and promotes lithium salt dissociation. Then, the YOP cluster chains are grafted with polyether amine and uniformly dispersed in the PVDF-HFP matrix via hydrogen bonds, significantly increasing the organic-inorganic interface area. Under the effect of strong local charge, the β-phase transformation of PVDF-HFP is induced for aligning dipoles of ─CF₂─ groups to optimize Li⁺ distribution and form continuous, oriented Li⁺ interface pathways. Consequently, the YOPSE exhibits high ionic conductivity (0.68 mS cm^-1), a lithium-ion transference number of 0.62, and excellent cycling stability (98.5% capacity retention of LFP/Li batteries after 800 cycles at 2C). This study demonstrates the synergetic effects of hetero-structure nanomaterials and polymer matrix, providing insights into solid-state battery designs.