Synthesis and Redox Mechanism of Cation-Disordered, Rock-Salt Cathode-Material Li-Ni-Ti-Nb-O Compounds for a Li-Ion Battery.

Cation-disordered oxide materials working as cathodes for Li-ion batteries have been at a standstill because of their structurally limited specific capacities (below 175 mAh g in most cases). In this work, we have introduced 4d Nb into host material LiNiTiO to synthesize Ni-based cation-disordered 3̅ Li-Ni-Ti-Nb-O compounds of LiNiTiNbO ( = 0, 5, 10, 15, 20) through a sol-gel method, showing particle sizes of less than 200 nm. Taking LiNiTiNbO with the best performance (an average voltage of ∼2.7 V and high discharge capacity of 221.5 mAh g) among oxides as a model, we study the relationship between the structure, morphology, redox mechanism, and electrochemical performance of cation-disordered oxides through a combination of X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption near-edge spectroscopy tests and in situ XRD with electrochemistry. The obtained results indicate that the improved capacity is mainly ascribed to Nb, which optimizes the Ni/Ni practical capacity and effectively stabilizes the O/O redox reaction. The results emphasize that Li-Ni-Ti-Nb-O compounds are promising members in the family of cation-disordered transition-metal oxide materials.