Hong, NingyunLi, JianweiGuo, ShihongHan, HuaweiWang, HaojiHu, XinyuHuang, Jiangnan2024-08-042024-08-0420232050-74882050-7496https://doi.org/10.1039/d3ta03640ehttps://hdl.handle.net/11616/101553O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) is one of the most representative cathode materials with low cost and high capacity advantages. However, the sluggish diffusion kinetics and severe cathode-electrolyte interfacial reaction are serious roadblocks to commercialization. Hereby, a novel method of in situ V-modification is well-designed to play dual roles in reconstructing the crystal lattice and interface structure. Notably, the broadened layer spacing of O-Na-O and shortened TM-O bond are attributed to successful doping of V5+ into the bulk, accelerating the transmission of sodium ions and improving the structure stability. Concomitantly, the construction of a thin surface coating layer is beneficial for mitigating volume expansion and inhibiting structural degradation, which is validated by in situ X-ray diffraction coupled with the synchrotron X-ray absorption spectroscopy. Consequently, the rationally designed V-modified NFM cathode exhibits excellent cycling performances, exhibiting great capacity retention of 75.8% after 500 cycles at 2C in a half cell, and 85.6% capacity retention is observed after 150 cycles at 1C in the full cell. This work provides new insights into the development of O3-type layered oxide cathodes toward long-cycle life applications for large-scale energy storage systems.eninfo:eu-repo/semantics/closedAccessO3-Type Layered OxideCathode MaterialsNa-IonMechanismArticle1135188721888010.1039/d3ta03640e2-s2.0-85169511692Q1WOS:001051449300001Q1