Fast and Durable Lithium Storage Enabled By Tuning Entropy in Wadsley-Roth Phase Titanium Niobium Oxides

Abstract

To date, Wadsley−Roth phase materials are one of the most promising intercalation-type hosts for fast lithium transport because of the unique crystalline diffusion channels. However, the volume expansion as well as sluggish ion/electron transport kinetics retards its application in grid scale. In recent years, various strategies have been suggested to further improve the overall performance of micro-sized Wadsley-Roth phase materials, such as oxygen vacancy creation or cation substitution.Lately, entropy tuning has received considerable interest due to the favorable entropy-dominated phase-stabilization and ionic conductivity boosting effects.[1,2] However, it has only been applied in a few materials and the understanding of its function is still limited. It has been suggested that entropy-stabilized Wadsley−Roth shear phases with a more ordered structure would be stable upon electrochemical lithium (de-)insertion without a phase transition, while a more disordered structure would compromise the stability of the active material.[3] Therefore, suitable entropy tuning in entropy-stabilized Wadsley−Roth phase materials remains challenging and detailed knowledge about its effect on crystal structure and lithium storage is still lacking.Here, we have successfully realized entropy-stabilized Wadsley-Roth phase Fe0.4Ti1.6Nb10O28.8 (FTNO) in which the increased entropy, due to iron substitution, leads to a reduced grain size, and therefore, a shortened Li+ diffusion channel length.[4] Secondly, the diffusion coefficient and the reaction rate constant are enhanced leading to a reduced overpotential and an improved rate performance. Benefiting from this, the micro-sized FTNO electrode exhibits an enhanced rate ability of 73.7 mAh·g-1 at 50 C as compared to 37.9 mAh·g-1 for its TNO counterpart. Thirdly, the increased entropy results in an extended cycling durability of FTNO electrode which can deliver a specific capacity of 130.0 mAh g-1 after 6000 cycles at high rate of 10 C. Operando XRD analysis demonstrates a suppression of the a-axis deformation during the first stage of the lithiation process. The mechanism is revealed by DFT calculations and found that Fe-O bond lengths undergo less changes than Ti-O during lithiation. Finally, the potential practical application of FTNO anodes has been demonstrated by successfully constructing fast charging and stable LiFePO4‖FTNO full cells.Our results demonstrate the effectiveness of tuning entropy by iron substitution to stabilize the Wadsley-Roth phase with fast charging ability, which can be extended to other intercalation electrodes for enhanced battery applications.[1] Y. Zeng et al., Science 2022, 378, 1320-1324.[2] R. Zhang et al., Nature 2022, 610, 67-73.[3] A. A. Voskanyan et al., Chem. Mater. 2020, 32, 5301-5308[4] J. Zheng et al., Small, smll.202301967R1, accepted.