The development of solid electrolytes (SEs) is a promising pathway to improve the energy density and safety of conventional Li-ion batteries. Several lithium chloride SEs, Li3MCl6 (M = Y, Er, In, and Sc), have gained popularity due to their high ionic conductivity, wide electrochemical window, and good chemical stability. This study systematically investigated 17 Li3MCl6 SEs to identify novel and promising lithium chloride SEs. Calculation results revealed that 12 Li3MCl6 (M = Bi, Dy, Er, Ho, In, Lu, Sc, Sm, Tb, Tl, Tm, and Y) were stable phase with a wide electrochemical stability window and excellent chemical stability against cathode materials and moisture. Li-ion transport properties were examined using bond valence site energy (BVSE) and ab initio molecular dynamics (AIMD) calculation. Li3MCl6 showed the lower migration energy barrier in monoclinic structures, while orthorhombic and trigonal structures exhibited higher energy barriers due to the sluggish diffusion along the two-dimensional path based on the BVSE model. AIMD results confirmed the slower ion migration along the 2D path, exhibiting lower ionic diffusivity and higher activation energy in orthorhombic and trigonal structures. For the further increase of ionic conductivity in monoclinic structures, Li-ion vacancy was formed by the substitution of M3+ with Zr4+. Zr-substituted phase (Li2.5M0.5Zr0.5Cl6, M = In, Sc) exhibited up to a fourfold increase in ionic conductivity. This finding suggested that the optimization of Li vacancy in the Li3MCl6 SEs could lead to superionic Li3MCl6 SEs.

Solid electrolytes (SEs) are promising candidates for enhancing the energy density and safety of conventional lithium-ion batteries. Recently, lithium thioantimonate iodide argyrodites have been regarded as promising SEs because of their high ionic conductivities and air-stability. In this study, we utilized highenergy ball milling to synthesize Ge-substituted thioantimonate argyrodites and achieved an ionic conductivity of 16.1 mS cm −1 for Li 6.5 Sb 0.5 Ge 0.5 S 5 I, which is the highest value among the reported cold-pressed SE pellets. First-principles calculations reveal that concerted Li-ion migrations through the inter-cage paths substantially improve the ionic conductivity. Li 6.5 Sb 0.5 Ge 0.5 S 5 I shows good compatibility with LiNi 0.5 Co 0.2 Mn 0.3 O 2 -based all-solid-state batteries (ASSBs) after applying Li 3 YCl 6 as a catholyte, which exhibits a high discharge capacity of 164 mAh g −1 and good cycle stability. Ge-substituted thioantimonate argyrodites exhibit excellent air-stability, which facilitates reducing the synthesis and fabrication costs of ASSBs with hygroscopic P-based sulfide SEs. The superionic conductors with high air-stability reported in this study demonstrate substantial promise for the development of ASSBs.

Lithium-based solid electrolytes have been investigated in many studies for improving the energy density and safety of conventional Li-ion batteries. Recently, Li argyrodites (Li6+x Sb1–x Si x S5I) have been reported as promising superionic conductors, exhibiting an ionic conductivity above 10 mS cm–1. This study examined the high ionic conductivities of Li6+x Sb1–x Si x S5I using first-principles calculations and subsequent experiments. The calculation results demonstrate that the Li ionic conductivities increase with the Si content in Li6+x Sb1–x Si x S5I due to the concerted Li-ion migration. Li6+x Sb1–x Si x S5I compounds synthesized using high-energy ball milling exhibit a high-symmetry argyrodite structure. The Li6.75Sb0.25Si0.75S5I phase demonstrates a favorable combination of a high ionic conductivity of 13.1 mS cm–1 and a low activation energy of 0.17 eV, which was achieved for the first time for cold-pressed pellets, leading to a high ionic conductivity at low temperatures (1.4 mS cm–1 at −20 °C). In addition, Li6.75Sb0.25Si0.75S5I exhibits good electrochemical stability, compatibility with Li metal anodes, high critical current density (1.5 mA cm–2), and hydrolysis stability. Based on the lightweight, low-cost, and non-toxic features of Si, the high Si content in superionic conductor Li6.75Sb0.25Si0.75S5I shows substantial promise for practical use in all-solid-state Li batteries.