A niobium oxide with a shear structure and planar defects for high-power lithium ion batteries

Abstract

The development of anode materials with high-rate capability is critical to high-power lithium batteries. T-Nb₂O₅ has been widely reported to exhibit pseudocapacitive behavior and fast lithium storage capability. However, the other polymorphs of Nb₂O₅ prepared at higher temperatures have the potential to achieve even higher specific capacity and tap density than T-Nb₂O₅, offering higher volumetric power and energy density. Here, micrometer-sized H-Nb₂O₅ with rich Wadsley planar defects (denoted as d-H-Nb₂O₅) is designed for fast lithium storage. The performance of H-Nb₂O₅ with local rearrangements of [NbO₆] octahedra blocks surpasses that of T-Nb₂O₅ in terms of specific capacity, rate capability, and stability. A wide range variation in the valence of niobium ions upon lithiation was observed for defective H-Nb₂O₅via operando X-ray absorption spectroscopy. Operando extended X-ray absorption fine structure and ex situ Raman spectroscopy analyses reveal a large and reversible distortion of the structure in the two-phase region. Computation and ex situ X-ray diffraction analysis reveal that the shear structure expands along major lithium diffusion pathways and contracts in the direction perpendicular to the shear plane. Planar defects relieve strain through perpendicular arrangements of blocks, minimizing volume change and enhancing structural stability. In addition, strong Li adsorption on planar defects enlarges intercalation capacity. Different from nanostructure engineering, our strategy to modify the planar defects in the bulk phase can effectively improve the intrinsic properties. The findings in this work offer new insights into the design of fast Li-ion storage materials in micrometer sizes through defect engineering, and the strategy is applicable to the material discovery for other energy-related applications.