Constructing Heterotransition Metal Ligand Field Clusters with a Compact Spatial Structure for Maintaining Unimpeded Sodium-Ion Migration

作者：Hanlin Wang, Jiajia An, Wenxi Zhao, Binkai Yu, Ye Li, Juntao Hu, Shikang Jiang, Qinfen Gu, Junwu Zhu, He Zhu, Jing‐Wen Sun, Limin Zhou, Shengjie Peng, Yuping Wu, Hui Xia, Mingzhe Chen · 发表于：ACS Nano · 年份：2025 · DOI：10.1021/acsnano.5c11413 · 被引用次数：5 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Supercapacitor Materials and Fabrication

Revealing the mechanism of Mn doping in polyanionic NaFePO 4 materials advances our fundamental understanding of electrochemical reactions. Herein, we propose the concept of heterotransition metal ligand field clusters (H-TMLFC) as a framework to investigate the structural evolution of transition metal (TM) ligand fields at the microscopic level. The introduced [MnO 6 ] octahedra exhibit a distinctive half-filled frontier orbital configuration, thereby strengthening σ-bonding interactions and modulating the charge distribution between adjacent [FeO 6 ] units. The redistribution of charge density around the edge-sharing oxygen atoms in [FeO 6 ]–[MnO 6 ] pairs enhances Fe–O covalency and mitigates Fe/Na antisite defects. As a result, H-TMLFC-derived NaFe 0.95 Mn 0.05 PO 4 achieves an exceptional capacity of 148.9 mAh·g –1 (96.7% of the theoretical capacity) and exhibits superior long-term cycling stability. This work introduces a novel approach for designing high-performance sodium-ion batteries through TM doping, offering atomic-scale insights into the optimization of polyanionic cathode materials.