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Operando synchrotron X-ray diffraction (XRD) studies have not previously been used to directly characterize Li metal in standard batteries due to the extremely weak scattering from Li atoms. In this work, it is demonstrated the stripping and plating of Li metal can be effectively quantified during battery cycling in appropriately designed synchrotron XRD experiments that utilize an anode-free battery configuration in which a Li-containing cathode material of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) is paired with a bare anode current collector consisting of either Cu metal (Cu/NMC) or Mo metal (Mo/NMC). In this configuration, it is possible to probe local variations in the deposition and stripping of Li metal with sufficient spatial sensitivity to map the inhomogeneity in pouch cells and to follow these processes with sufficient time resolution to track state-of-charge-dependent variations in the rate of Li usage at a single point. For the Cu/NMC and Mo/NMC batteries, it was observed that the initial plating of Li occurred in a very homogeneous manner but that severe macroscopic inhomogeneity arose on a mm-scale during the subsequent stripping of Li, contrasting with the conventional wisdom that the greatest challenges in Li metal batteries are associated with Li deposition. 

V 2 O 5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V 2 O 5 ) and in its metastable tunnel structure (ζ-V 2 O 5 ). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized ( ca . 100 nm) ζ-V 2 O 5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V 2 O 5 . This effect results in a significant boost in stable discharge capacity (130 mA h g −1 ) compared to bulk ζ-V 2 O 5 (70 mA h g −1 ), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V 2 O 5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases. 

Antiperovskite structure compounds (X₃AB, where X is an alkali cation and A and B are anions) have the potential for highly correlated motion between the cation and a cluster anion on the A or B site. This so‐called “paddle‐wheel” mechanism may be the basis for enhanced cation mobility in solid electrolytes. Through combined experiments and modeling, the first instance of a double paddle‐wheel mechanism, leading to fast sodium ion conduction in the antiperovskite Na_3−xO_1−x(NH₂)_x(BH₄), is shown. As the concentration of amide (NH₂⁻) cluster anions is increased, large positive deviations in ionic conductivity above that predicted from a vacancy diffusion model are observed. Using electrochemical impedance spectroscopy, powder X‐ray diffraction, synchrotron X‐ray diffraction, neutron diffraction, ab initio molecular dynamics simulations, and NMR, the cluster anion rotational dynamics are characterized and it is found that cation mobility is influenced by the rotation of both NH₂⁻and BH₄⁻species, resulting in sodium ion conductivity a factor of 10²higher atx = 1 than expected for the vacancy mechanism alone. Generalization of this phenomenon to other compounds could accelerate fast ion conductor exploration and design.