Manipulated Fluoro‐Ether Derived Nucleophilic Decomposition Products for Mitigating Polarization‐Induced Capacity Loss in Li‐Rich Layered Cathode

Abstract Electrolyte engineering is a fascinating choice to improve the performance of Li‐rich layered oxide cathodes (LRLO) for high‐energy lithium‐ion batteries. However, many existing electrolyte designs and adjustment principles tend to overlook the unique challenges posed by LRLO, particularly the nucleophilic attack. Here, we introduce an electrolyte modification by locally replacing carbonate solvents in traditional electrolytes with a fluoro‐ether. By benefit of the decomposition of fluoro‐ether under nucleophilic O‐related attacks, which delivers an excellent passivation layer with LiF and polymers, possessing rigidity and flexibility on the LRLO surface. More importantly, the fluoro‐ether acts as “sutures”, ensuring the integrity and stability of both interfacial and bulk structures, which contributed to suppressing severe polarization and enhancing the cycling capacity retention from 39 % to 78 % after 300 cycles for the 4.8 V‐class LRLO. This key electrolyte strategy with comprehensive analysis, provides new insights into addressing nucleophilic challenge for high‐energy anionic redox related cathode systems.