Nano‐Confined Synergistic Conduction Enables Electrolytes for All‐Solid‐State Lithium Metal Batteries

作者：Chi Han, Huasen Shen, Mengjun Li, Yunan Tian, Yuxuan Chen, Xiaoxin Wu, Jiaqi Sun, Liwen Liu, Xuanxuan Zhang, Jian Tang, Yu He, Yuyu Li, Ming Xie, Zhaohuai Li · 发表于：Advanced Functional Materials · 年份：2025 · DOI：10.1002/adfm.202523139 · 被引用次数：5 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Advanced Battery Technologies Research

Abstract An ultrathin (15 µm) composite polymer solid‐state electrolyte is engineered by embedding a dual‐polymer matrix (PEO/PVDF‐HFP) and nano‐LATP particles within a negatively charged nanofiber scaffold (PPLNF). This architecture enables a nano‐confined synergistic conduction (NCSC) mechanism, which electrostatic repulsion from functionalized pore walls excludes TFSI − anions, while LATP promotes LiTFSI dissociation and chemically anchors anions via Lewis acid sites. This dual action localizes anions and elevates free lithium ion (Li⁺) concentration/mobility, while low‐crystallinity polymer segments synergize with the scaffold to form efficient Li⁺ transport channels. The PPLNF achieves high ionic conductivity (1.04 × 10 −3 S cm −1 at 25 °C), Li⁺ transference number (0.75), and electrochemical stability (>5.0 V). It demonstrates exceptional interfacial compatibility, dendrite‐free Li anode cycling over 1000 h, and a critical current density of 2.0 mA cm −2 . NCM811||PPLNF||Li full cells retain >90% capacity after 200 cycles. This work establishes NCSC as a new paradigm for designing high‐performance solid‐state electrolytes toward next‐generation lithium metal batteries.