An in situ dual-modification strategy for O3-NaNi1/3Fe1/3Mn1/3O2 towards high-performance sodium-ion batteries

Abstract

O3-type NaNi_1/3Fe_1/3Mn_1/3O₂ (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.