Rapid and Reversible Lithium Insertion in the Wadsley–Roth-Derived Phase NaNb(13)O(33)

[Image: see text] The development of new high-performing battery materials is critical for meeting the energy storage requirements of portable electronics and electrified transportation applications. Owing to their exceptionally high rate capabilities, high volumetric capacities, and long cycle lives, Wadsley–Roth compounds are promising anode materials for fast-charging and high-power lithium-ion batteries. Here, we present a study of the Wadsley–Roth-derived NaNb(13)O(33) phase and examine its structure and lithium insertion behavior. Structural insights from combined neutron and synchrotron diffraction as well as solid-state nuclear magnetic resonance (NMR) are presented. Solid-state NMR, in conjunction with neutron diffraction, reveals the presence of sodium ions in perovskite A-site-like block interior sites as well as square-planar block corner sites. Through combined experimental and computational studies, the high rate performance of this anode material is demonstrated and rationalized. A gravimetric capacity of 225 mA h g(–1), indicating multielectron redox of Nb, is accessible at slow cycling rates. At a high rate, 100 mA h g(–1) of capacity is accessible in 3 min for micrometer-scale particles. Bond-valence mapping suggests that this high-rate performance stems from fast multichannel lithium diffusion involving octahedral block interior sites. Differential capacity analysis is used to identify optimal cycling rates for long-term performance, and an 80% capacity retention is achieved over 600 cycles with 30 min charging and discharging intervals. These initial results place NaNb(13)O(33) within the ranks of promising new high-rate lithium-ion battery anode materials that warrant further research.