Lithium-ion intercalation by coupled ion-electron transfer

• 成果类型: Article
• 署名作者: Zhang, Yirui; Fraggedakis, Dimitrios; Gao, Tao; Pathak, Shakul; Zhuang, Debbie; Grosu, Cristina; Samantaray, Yash; Neto, Armando R. C.; Duggirala, Sravani R.; Huang, Botao; Zhu, Yun Guang; Giordano, Livia; Tatara, Ryoichi; Agarwal, Harsh; Stephens, Ryan M.; Bazant, Martin Z.; Shao-Horn, Yang
• 署名单位: Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT); Royal Dutch Shell; Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT); Columbia University; University of Milano-Bicocca; Yokohama National University
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-8075; 1095-9203
• DOI: 10.1126/science.adq2541
• 发表日期: 2025-10-02
• 页码: eadq2541
• 关键词: CHARGE-TRANSFER KINETICS; transport-properties; electrochemical properties; temperature-dependence; cathode materials; phase-separation; METAL TRANSITION; self-diffusion; licoo2; battery

摘要

The underlying reaction mechanism in lithium-ion batteries remains poorly understood. We provide experimental and theoretical evidence that lithium intercalation occurs by coupled ion-electron transfer, where ion transfer across the electrode-electrolyte interface is facilitated by electron transfer to a neighboring redox site. Electrochemical measurements for a variety of common electrode and electrolyte materials reveal a universal dependence of the (de-)intercalation rate on Li+ vacancy fraction, as well as temperature and electrolyte effects consistent with the theory, which could be used to guide the molecular design of lithium-ion battery interfaces.