In cation-disordered rocksalt Li-ion cathode materials, an excess of Li with respect to the transition metal content is necessary for the creation of percolating pathways for Li transport. Because of the lower amount of redox-active transition metal, a substantial part of the charge transfer must occur via less reversible oxygen redox. Fluorination can be used to minimize this dependence on oxygen redox by increasing the amount of low-valent transition metal in the compound, but it adds complexity to materials design. Here, we investigate the feasibility of using computationally constructed phase diagrams to facilitate the search for optimal oxyfluorides. We use the phase diagram of LiF–Li₃NbO₄–NiO to identify Li_1.13Ni_0.57Nb_0.3O_1.75F_0.25 and Li_1.19Ni_0.59Nb_0.22O_1.46F_0.54 as two promising compositions and demonstrate that they can be successfully synthesized. These compounds exhibit significantly reduced hysteresis and higher energy density than the previously reported Li_1.3Ni_0.27Nb_0.43O₂ compound in this space. Although we generally attribute the improved performance to the increased Ni content enabled by fluorination, a more nuanced relation between fluorination and the cycling behavior is revealed through electrochemical tests, X-ray absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and density functional theory. We find that fluorination increases the voltage, improves cycle life, but reduces the accessibility of Ni redox. Consideration of these effects will facilitate the future design of optimized disordered-rocksalt oxyfluoride cathodes.

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.

Altermagnetism was very recently identified as a new type of magnetic phase beyond the conventional dichotomy of ferromagnetism (FM) and antiferromagnetism (AFM). Its globally compensated magnetization and directional spin polarization promise new properties such as spin-polarized conductivity, spin-transfer torque, anomalous Hall effect, tunneling, and giant magnetoresistance that are highly useful for the next-generation memory devices, magnetic detectors, and energy conversion. Though this area has been historically led by the thin-film community, the identification of altermagnetism ultimately relies on precise magnetic structure determination, which can be most efficiently done in bulk materials. Our review, written from a materials chemistry perspective, intends to encourage materials and solid-state chemists to make contributions to this emerging topic through new materials discovery by leveraging neutron diffraction to determine the magnetic structures as well as bulk crystal growth for exploring exotic properties. We first review the symmetric classification for the identification of altermagnets with a summary of chemical principles and design rules, followed by a discussion of the unique physical properties in relation to crystal and magnetic structural symmetry. Several major families of compounds in which altermagnets have been identified are then reviewed. We conclude by giving an outlook for future directions.

Halides are promising solid-state electrolytes for all-solid-state lithium batteries due to their exceptional oxidation stability, high Li-ion conductivity, and mechanical deformability. However, their practicality is limited by the reliance on rare and expensive metals. This study investigates the Li₂MgCl₄ inverse spinel system as a cost-effective alternative. Molecular dynamics simulations reveal that lithium disordering at elevated temperatures significantly reduces the activation energy in Li₂MgCl₄. To stabilize this disorder at lower temperatures, we experimentally explored the Li _x Zr_1-x/2Mg _x/2Cl₄ system and found that Zr doping induces both Zr and Li disorder at the 16c site at room temperature (RT). This leads to a 2 order-of-magnitude increase in ionic conductivity for the Li_1.25Zr_0.375Mg_0.625Cl₄ composition, achieving 1.4 × 10^-5 S cm^-1 at RT, compared to pristine Li₂MgCl₄. By deconvoluting the role of lithium vacancies and dopants, we reveal that cation disordering to the 16c site predominantly enhances ionic conductivity, whereas lithium vacancy concentration has a very limited effect.