Gradient Interphase Engineering Enabled by Anionic Redox for High-Voltage and Long-Life Li-Ion Batteries

作者：Baodan Zhang, Xiaohong Wu, Haiyan Luo, Hao Yan, Yilong Chen, Shiyuan Zhou, Jianhua Yin, Kang Zhang, Hong‐Gang Liao, Qingsong Wang, Yeguo Zou, Yu Qiao, Shi‐Gang Sun · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c11440 · 被引用次数：101 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Advanced Battery Technologies Research

Intelligent utilization of the anionic redox reaction (ARR) in Li-rich cathodes is an advanced strategy for the practical implementation of next-generation high-energy-density rechargeable batteries. However, due to the intrinsic complexity of ARR (e.g., nucleophilic attacks), the instability of the cathode-electrolyte interphase (CEI) on a Li-rich cathode presents more challenges than typical high-voltage cathodes. Here, we manipulate CEI interfacial engineering by introducing an all-fluorinated electrolyte and exploiting its interaction with the nucleophilic attack to construct a gradient CEI containing a pair of fluorinated layers on a Li-rich cathode, delivering enhanced interfacial stability. Negative/detrimental nucleophilic electrolyte decomposition has been efficiently evolved to further reinforce CEI fabrication, resulting in the construction of LiF-based indurated outer shield and fluorinated polymer-based flexible inner sheaths. Gradient interphase engineering dramatically improved the capacity retention of the Li-rich cathode from 43 to 71% after 800 cycles and achieved superior cycling stability in anode-free and pouch-type full cells (98.8% capacity retention, 220 cycles), respectively.