Lithium-Ion Diffusivity Increases with Block Size in Niobium Tungsten Oxide Shear Structures

Nb₁₆W₅O₅₅ emerged as a high-rate anode material for Li-ion batteries in 2018 (Griffith et al.,Nature2018, 559 (7715), 556–563). This exciting discovery ignited research in Wadsley-Roth (W-R) compounds, but systematic experimental studies have not focused on how to tune material chemistry and structure to achieve desirable properties for energy storage applications. In this work, we systematically investigate how structure and composition influences capacity, Li-ion diffusivity, charge-discharge profiles, and capacity loss in a series of niobium tungsten oxide W-R compounds: (3×4)-Nb₁₂WO₃₃, (4×4)-Nb₁₄W₃O₄₄, and (4×5)-Nb₁₆W₅O₅₅. Potentiostatic intermittent titration (PITT) data confirmed that Li-ion diffusivity increases with block size, which can be attributed to an increasing number of tunnels for Li-ion diffusion. The small (3×4)-Nb₁₂WO₃₃ block size compound with preferential W ordering on tetrahedral sites exhibits single electron redox and, therefore, the smallest measured capacity despite having the largest theoretical capacity. This observation signals that introducing cation disorder (W occupancy at the octahedral sites in the block center) is a viable strategy to access multi-electron redox behavior in (3×4) Nb₁₂WO₃₃. The asymmetric block size compounds (i.e., (3×4) and (4×5) blocks) exhibit the greatest capacity loss after the first cycle, possibly due to Li-ion trapping at a unique low energy pocket site along the shear plane. Finally, the slope of the charge-discharge profile increases with increasing block size, likely because the total number of energy-equivalent Li-ion binding sites also increases. This unfavorable characteristic prohibits the large block sizes from delivering constant power at a fixed C-rate more so than the smaller block sizes. Based on these findings, we discuss design principles for Li-ion insertion hosts made from W-R materials.