Adsorptive Shield Derived Cathode Electrolyte Interphase Formation with Impregnation on LiNi_0.8Mn_0.1Co_0.1O₂ Cathode: A Mechanism-Guiding-Experiment Study

Lithium difluoro(oxalate) borate (LiDFOB) contributes actively to cathode–electrolyte interface (CEI) formation, particularly safeguarding high-voltage cathode materials. However, LiNi x Co z Mn y O 2 -based batteries benefit from the LiDFOB and its derived CEI only with appropriate electrolyte design while a comprehensive understanding of the underlying interfacial mechanisms remains limited, which makes the rational design challenging. By performing ab initio calculations, the CEI evolution on the LiNi 0.8 Co 0.1 Mn 0.1 O 2 has been investigated. The findings demonstrate that LiDFOB readily adheres to the cathode via semidissociative configuration, which elevates the Li deintercalation voltage and remains stable in solvent. Electrochemical processes are responsible for the subsequent cleavage of B–F and B–O bonds, while the B–F bond cleavage leading to LiF formation is dominant in the presence of adequate Li + with a substantial Li intercalation energy. Thus, impregnation is established as an effective method to regulate the conversion channel for efficient CEI formation, which not only safeguards the cathode’s structure but also counters electrolyte decomposition. Consequently, in comparison to utilizing LiDFOB as an electrolyte additive, employing LiDFOB impregnation in the NCM811/Li cell yields significantly improved cycling stability for over 2000 h.