Kira E. Wyckoff

Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti₂Nb₁₀O₂₉ and metallic Nb₁₂O₂₉. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti₂Nb₁₀O₂₉ contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb₁₂O₂₉ a slightly better electrode material for long-term cycling at slower rates.

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 NaNb₁₃O₃₃ 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 NaNb₁₃O₃₃ within the ranks of promising new high-rate lithium-ion battery anode materials that warrant further research.

Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with Pb^II (such as Sb^III and Bi^III). Here, we report eight HLDP halides from the A₂M^IM^IIIX₈ family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); M^I = Cu or Ag; M^III = Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)₂Ag^IRu^IIICl₈ and (PPDA)₂Ag^IMo^IIICl₈ show no obvious evidence of a magnetic ordering transition. While the t_2g³ Mo^III compound displays Curie–Weiss behavior for a spin-only d³ ion, the t_2g⁵ Ru^III compound displays marked deviations from the Kotani theory.

Electrode materials for Li⁺-ion batteries require optimization along several disparate axes related to cost, performance, and sustainability. One of the important performance axes is the ability to retain structural integrity though cycles of charge/discharge. Metal–metal bonding is a distinct feature of some refractory metal oxides that has been largely underutilized in electrochemical energy storage, but that could potentially impact structural integrity. Here LiScMo₃O₈, a compound containing triangular clusters of metal–metal bonded Mo atoms, is studied as a potential anode material in Li⁺-ion batteries. Electrons inserted though lithiation are localized across rigid Mo₃ triangles (rather than on individual metal ions), resulting in minimal structural change as suggested by operando diffraction. The unusual chemical bonding allows this compound to be cycled with Mo atoms below a formally +4 valence state, resulting in an acceptable voltage regime that is appropriate for an anode material. Several characterization methods including potentiometric entropy measurements indicate two-phase regions, which are attributed through extensive first-principles modeling to Li⁺ ordering. This study of LiScMo₃O₈ provides valuable insights for design principles for structural motifs that stably and reversibly permit Li⁺ (de)insertion.