Fast and Durable Lithium Storage Enabled by Tuning Entropy in Wadsley–Roth Phase Titanium Niobium Oxides

Abstract

Wadsley-Roth phase titanium niobium oxides have received considerable interest as anodes for lithium ion batteries. However, the volume expansion and sluggish ion/electron transport kinetics retard its application in grid scale. Here, fast and durable lithium storage in entropy-stabilized Fe_0.4 Ti_1.6 Nb₁₀ O_28.8 (FTNO) is enabled by tuning entropy via Fe substitution. By increasing the entropy, a reduction of the calcination temperature to form a phase pure material is achieved, leading to a reduced grain size and, therefore, a shortening of Li⁺ pathway along the diffusion channels. Furthermore, in situ X-ray diffraction reveals that the increased entropy leads to the decreased expansion along a-axis, which stabilizes the lithium intercalation channel. Density functional theory modeling indicates the origin to be the more stable FeO bond as compared to TiO bond. As a result, the rate performance is significantly enhanced exhibiting a reversible capacity of 73.7 mAh g^-1 at 50 C for FTNO as compared to 37.9 mAh g^-1 for its TNO counterpart. Besides, durable cycling is achieved by FTNO, which delivers a discharge capacity of 130.0 mAh g^-1 after 6000 cycles at 10 C. Finally, the potential impact for practical application of FTNO anodes has been demonstrated by successfully constructing fast charging and stable LiFePO₄ ‖FTNO full cells.