Facile Synthesis of Inorganic Li2B12H12/LiI Solid Electrolytes for High‐Voltage All‐Solid‐State Lithium Batteries

作者：Deliang Xu, Mengyuan Jin, Zilong Su, Ran Liu, Mingchuan Xiang, Wanggang Fang, Liqing He, Renbing Wu, Yanhui Guo · 发表于：Advancement of science · 年份：2025 · DOI：10.1002/advs.202510193 · 被引用次数：3 · 研究领域：Medicine

Hydroborate‐based solid electrolytes (SEs), distinguished by their eco‐friendliness and non‐flammability have emerged as a research hotspot in energy storage research. Despite these advantages, their widespread adoption is constrained by insufficient ionic conductivity and poor high‐voltage compatibility. To overcome this challenge, a novel hydroborate SEs, 400‐0.6Li2B12H12‐0.4LiI (denoted as 400‐0.6B12‐0.4I), is engineered through a facile synthesis strategy combining high‐temperature processing (400 °C, 2 h, in Ar) and LiI doping. 400‐0.6B12‐0.4I exhibits an outstanding ionic conductivity up to 0.75 mS cm−1 at 25 °C, which is the highest level among the reported inorganic Li2B12H12‐based SEs so far. It also improves the cycling stability against lithium metal anodes, limits dendrite growth with a high critical current density of 5.0 mA cm−2, which enables the Li symmetrical cells to cycle over 1000 h at 25 °C with only 10 mV of overpotential. Moreover, it cycles well in cells using lithium anodes and various high voltage (>4 V vs Li+/Li) cathodes materials such as LiCoO2, NCM811, and LiMn2O4. The proposed 400‐0.6B12‐0.4I SEs offer valuable guidance for designing next‐generation lithium‐ion solid electrolytes with superior ionic conductivity, enhanced interfacial stability, and exceptional electrode compatibility.