Surface Chemical Coordination Stabilizes Ni-Rich Cathodes for High-Energy Li-Metal Batteries

作者：Jinze Wang, Shuo‐Qing Zhang, Ruhong Li, Long Chen, Haikuo Zhang, Baochen Ma, Sen Jiang, Tao Zhou, Jiajie Huang, Haotian Zhu, Long Li, Lixin Chen, Tao Deng, Xiulin Fan · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.4c16406 · 被引用次数：26 · 研究领域：Advanced Battery Materials and Technologies、Advancements in Battery Materials、Extraction and Separation Processes

The stability of the electrode–electrolyte interface is a critical factor influencing the electrochemical performance of Li-metal batteries. However, on the delithiated Ni-rich cathode surface, the strong catalytic effects of transition metals with coordination deficiency significantly aggravate the parasitic reactions with Li-metal-compatible ether-based electrolytes, thereby reducing the cycling stability of high-voltage Ni-rich batteries. Here, we propose an sp 2 -induction mechanism to address coordination deficiency through the coupling of interfacial orbitals between molecules and the cathode surface. Sp 2 -hybrid high-fluorinated olefins, characterized by unsaturated bonds, exhibit highly delocalized electronic properties (electron delocalization index >0.95 au) and elevated anodic stability (ionization potential >10 eV). These characters ensure robust and stable interactions with the Ni-rich cathode, facilitating the formation of induced orbitals. These low-energy orbitals accommodate Ni 3 d electrons, effectively mitigating the interfacial coordination deficiency and inhibiting surface side reactions. Among the sp 2 -hybrid high-fluorinated olefins, (perfluorobutyl)ethylene (PFBE) is identified as an optimal inducing molecule due to its strongest interaction and excellent coordination complementarity on the cathode surface. The PFBE-based electrolyte significantly alleviates the degradation of cathode surface structure and demonstrates remarkable cyclic stability, ac...