Ambient-air-stable Li3InCl6 halide solid electrolyte, with high ionic conductivity of 1.49 × 10−3 S cm−1 at 25 °C, delivers essential advantages over commercial sulfide-based solid electrolyte.

The enabling of high energy density of all-solid-state lithium batteries (ASSLBs) requires the development of highly Li+-conductive solid-state electrolytes (SSEs) with good chemical and electrochemical stability. Recently, halide SSEs based on different material design principles have opened new opportunities for ASSLBs. Here, we discovered a series of Li x ScCl3+x SSEs (x = 2.5, 3, 3.5, and 4) based on the cubic close-packed anion sublattice with room-temperature ionic conductivities up to 3 × 10–3 S cm–1. Owing to the low eutectic temperature between LiCl and ScCl3, Li x ScCl3+x SSEs can be synthesized by a simple co-melting strategy. Preferred orientation is observed for all the samples. The influence of the value of x in Li x ScCl3+x on the structure and Li+ diffusivity were systematically explored. With increasing x value, higher Li+, lower vacancy concentration, and less blocking effects from Sc ions are achieved, enabling the ability to tune the Li+ migration. The electrochemical performance shows that Li3ScCl6 possesses a wide electrochemical window of 0.9–4.3 V vs Li+/Li, stable electrochemical plating/stripping of Li for over 2500 h, as well as good compatibility with LiCoO2. LiCoO2/Li3ScCl6/In ASSLB exhibits a reversible capacity of 104.5 mAh g–1 with good cycle life retention for 160 cycles. The observed changes in the ionic conductivity and tuning of the site occupations provide an additional approach toward the design of better SSEs.

To promote the development of solid‐state batteries, polymer‐, oxide‐, and sulfide‐based solid‐state electrolytes (SSEs) have been extensively investigated. However, the disadvantages of these SSEs, such as high‐temperature sintering of oxides, air instability of sulfides, and narrow electrochemical windows of polymers electrolytes, significantly hinder their practical application. Therefore, developing SSEs that have a high ionic conductivity (>10−3 S cm−1), good air stability, wide electrochemical window, excellent electrode interface stability, low‐cost mass production is required. Herein we report a halide Li+ superionic conductor, Li3InCl6, that can be synthesized in water. Most importantly, the as‐synthesized Li3InCl6 shows a high ionic conductivity of 2.04×10−3 S cm−1 at 25 °C. Furthermore, the ionic conductivity can be recovered after dissolution in water. Combined with a LiNi0.8Co0.1Mn0.1O2 cathode, the solid‐state Li battery shows good cycling stability.

Sulfide‐based solid‐state electrolytes (SSEs) for all‐solid‐state Li metal batteries (ASSLMBs) are attracting significant attention due to their high ionic conductivity, inherently soft properties, and decent mechanical strength. However, the poor incompatibility with Li metal and air sensitivity have hindered their application. Herein, the Sn (IV) substitution for P (V) in argyrodite sulfide Li6PS5I (LPSI) SSEs is reported, in the preparation of novel LPSI‐xSn SSEs (where x is the Sn substitution percentage). Appropriate aliovalent element substitutions with larger atomic radius (R > R

) provides the optimized LPSI‐20Sn electrolyte with a 125 times higher ionic conductivity compared to that of the LPSI electrolyte. The high ionic conductivity of LPSI‐20Sn enables the rich I‐containing electrolyte to serve as a stabilized interlayer against Li metal in sulfide‐based ASSLMBs with outstanding cycling stability and rate capability. Most importantly, benefiting from the strong Sn–S bonding in Sn‐substituted electrolytes, the LPSI‐20Sn electrolyte shows excellent structural stability and improved air stability after exposure to O2 and moisture. The versatile Sn substitution in argyrodite LPSI electrolytes is believed to provide a new and effective strategy to achieve Li metal‐compatible and air‐stable sulfide‐based SSEs for large‐scale applications.

Experimental section, magnified regions of the XRD patterns, supplemental XPS results, Raman spectra, impedance plots, DC polarization curves, SEM characterizations, ToF-SIMS chemical images, electrochemical performance, and summarized tables for making comparisons (PDF)