Molecular‐Bridging Interfacial Engineering to Reinforce Li‐Rich Cathodes

ABSTRACT Achieving both high uniformity and sufficient compactness in the surface coating of cathode materials remains a fundamental challenge, as uniformity dictates the suppression of interfacial side reactions and structural degradation, while compactness governs ionic transport kinetics and mechanical integrity against volumetric strain during prolonged cycling. Herein, we develop an in situ molecular‐bridging interfacial engineering strategy that constructs a uniform and compact lithium silicate (Li x SiO y , ∼2 nm) layer through electrostatic self‐assembly on Li‐rich layered cathode surfaces. In situ gas evolution analysis, structural characterization and theoretical simulations demonstrate that the molecular bridges formed between silane and the cathode surface effectively promote a more homogeneous surface electric‐field distribution and reinforce interfacial stability during electrochemical cycling. Consequently, the resulting cathode delivers markedly enhanced cycling stability, with a 22.7% improvement in capacity retention after 200 cycles, and superior rate capability with a capacity over 112 mAh g −1 at 5 C. Moreover, when deployed in a practical pouch full cell, it achieves more stable long‐term cycling. This work offers a molecular‐bridging interfacial engineering perspective for the rational design of high‐energy‐density cathode materials.