A Functional Air-Stable Li9.8GeP1.7Sb0.3S11.8I0.2 Superionic Conductor for High-Performance All-Solid-State Lithium Batteries.

Abstract

Solid-state electrolytes (SSEs) based on sulfides have become a subject of great interest due to their superior Li-ion conductivity, low grain boundary resistance, and adequate mechanical strength. However, they grapple with chemical instability toward moisture hypersensitivity, which decreases their ionic conductivity, leading to more processing requirements. Herein, a Li9.8GeP1.7Sb0.3S11.8I0.2 (LGPSSI) superionic conductor is designed with a Li+ conductivity of 6.6 mS cm-1 and superior air stability based on hard and soft acids and bases (HSAB) theory. The introduction of optimal antimony (Sb) and iodine (I) into the Li10GeP2S12 (LGPS) structure facilitates fast Li-ion migration with low activation energy (Ea) of 20.33 kJ mol-1. The higher air stability of LGPSSI is credited to the strategic substitution of soft acid Sb into (Ge/P)S4 tetrahedral sites, examined by Raman and X-ray photoelectron spectroscopy techniques. Relatively lower acidity of Sb compared to phosphorus (P) realizes a stronger Sb-S bond, minimizing the evolution of toxic H2S (0.1728 cm3 g-1), which is ∼3 times lower than pristine LGPS when LGPSSI is exposed to moist air for 120 min. The NCA//Li-In full cell with a LGPSSI superionic conductor delivered the first discharge capacity of 209.1 mAh g-1 with 86.94% Coulombic efficiency at 0.1 mA cm-2. Furthermore, operating at a current density of 0.3 mA cm-2, LiNbO3@NCA/LGPSSI/Li-In cell demonstrated an exceptional reversible capacity of 117.70 mAh g-1, retaining 92.64% of its original capacity over 100 cycles.