Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions (often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li1.1Mn0.8Ti0.1O1.9F0.1, an ultrahigh capacity of ≈320 mAh g−1 (energy density of ≈900 Wh kg−1) can be obtained through dynamic structural rearrangements upon cycling, along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn4+ and Li+ vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn4+ reduction, along with Li+ insertion transform the structure to a partially ordered DRX phase with a β′-LiFeO2-type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials.

The recently developed Li-excess cation-disordered rock salts (DRXs) exhibit an excellent chemical diversity for the development of alternative Co/Ni-free high-energy cathodes. Herein, the synthesis of a highly fluorinated DRX cathode, Li1.2Mn0.6Ti0.2O1.8F0.2, based on cost-effective and earth-abundant transition metals, via a solid-state reaction, is reported. The fluorinated DRX cathode using ammonium fluoride precursor exhibits more uniform particle size and delivers a specific discharge capacity of 233 mAh g−1 and specific energy of 754 Wh kg−1, with 206 mAh g−1 retained after 200 cycles. The combined synchrotron X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy analysis reveals that the remarkable cycling performance is attributed to the high fluorination and thus enhanced Mn content, enabling the utilization of more Mn redox than the oxide analog. This study demonstrates a great promise to develop next-generation cost-effective DRX cathodes with enhanced capacity retention for high-energy Li-ion batteries.

In the pursuit of urgently needed, energy dense solid-state batteries for electric vehicle and portable electronics applications, halide solid electrolytes offer a promising path forward with exceptional compatibility against high-voltage oxide electrodes, tunable ionic conductivities, and facile processing. For this family of compounds, synthesis protocols strongly affect cation site disorder and modulate Li⁺ mobility. In this work, we reveal the presence of a high concentration of stacking faults in the superionic conductor Li₃YCl₆ and demonstrate a method of controlling its Li⁺ conductivity by tuning the defect concentration with synthesis and heat treatments at select temperatures. Leveraging complementary insights from variable temperature synchrotron X-ray diffraction, neutron diffraction, cryogenic transmission electron microscopy, solid-state nuclear magnetic resonance, density functional theory, and electrochemical impedance spectroscopy, we identify the nature of planar defects and the role of nonstoichiometry in lowering Li⁺ migration barriers and increasing Li site connectivity in mechanochemically synthesized Li₃YCl₆. We harness paramagnetic relaxation enhancement to enable ⁸⁹Y solid-state NMR and directly contrast the Y cation site disorder resulting from different preparation methods, demonstrating a potent tool for other researchers studying Y-containing compositions. With heat treatments at temperatures as low as 333 K (60 °C), we decrease the concentration of planar defects, demonstrating a simple method for tuning the Li⁺ conductivity. Findings from this work are expected to be generalizable to other halide solid electrolyte candidates and provide an improved understanding of defect-enabled Li⁺ conduction in this class of Li-ion conductors.

Correction to: Nature Materialshttps://doi.org/10.1038/s41563-024-01800-8, published online 2 February 2024. In the version of the article initially published, the x axes in Figs. 2b,d and 5a,b originally read “T−1 (K−1)” and have now been amended to “1000 T−1 (K−1)” in the HTML and PDF versions of the article.

Oxides with a face-centred cubic (fcc) anion sublattice are generally not considered as solid-state electrolytes as the structural framework is thought to be unfavourable for lithium (Li) superionic conduction. Here we demonstrate Li superionic conductivity in fcc-type oxides in which face-sharing Li configurations have been created through cation over-stoichiometry in rocksalt-type lattices via excess Li. We find that the face-sharing Li configurations create a novel spinel with unconventional stoichiometry and raise the energy of Li, thereby promoting fast Li-ion conduction. The over-stoichiometric Li-In-Sn-O compound exhibits a total Li superionic conductivity of 3.38 × 10^-4 S cm^-1 at room temperature with a low migration barrier of 255 meV. Our work unlocks the potential of designing Li superionic conductors in a prototypical structural framework with vast chemical flexibility, providing fertile ground for discovering new solid-state electrolytes.