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International audience; Ion-conducting chalcogenide glass is a promising solid electrolyte with excellent conductivity and energy density for all-solid-state batteries. A suitable ionic channel for carriers in the amorphous network is urgently needed. In this work, the structural evolution of co-doped metal cations (Ge and Ga) in the glass matrix and its influence on electrochemical behavior were studied using a series of GexGa16-xSb64S128-40AgI glass samples. The macroscopic properties of samples were examined by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and Raman tests. The electrochemical behavior of samples was investigated by AC impendence spectroscopy and cyclic voltammetry (CV) measurement. Furthermore, a deliquescence experiment was applied for the chemical stability test of glass samples. The ionic conductivity of samples was developed by adding Ga components. Notably, the electrochemical window of electrolytes was remarkably wide at approximately 5 V. The resistance of samples to humidity was characterized by the decreased Raman peaks. Analysis results show that the Ga-related bonding structure evidently increased the chemical stability compared with the non-Ga sample. This work provides an insight into the effective and stable ions transport, especially in the Ge(Ga)SbS glass system. These results promote the further investigation of sulfide solid electrolytes and practical application of all-solid-state batteries.

International audience; The use of ion-conducting chalcogenide glass, a promising solid electrolyte, is encouraged at higher conductivity for all-solid-state rechargeable battery. Herein, a new quaternary glass of GaGeSbS–AgI system was successfully prepared, and its structural and electrochemical properties were investigated by XRD, Raman, and AC impendence measurement. The relatively high conductivity of 2.955 × 10−3 S/cm and low activation energy of 0.07 eV were obtained after optimized structure regulation. The short-range schematic of the glass structure was explored to determine the fast-migrating mechanism involved in conducting Ag+ ions. By controlling the proper ratio of Ga(Ge) and Sb cations, the loose and porous layer structure of [SbSxI3-x] linking by the [Ga(Ge)S4] tetrahedron was formed, resulting in the rapid transport of Ag+ ions with a reduced migration energy barrier. The current work is the first time that a sulfide solid electrolyte in quaternary glass system with desirable electrochemical characteristics was used to address energy and safety issues. © 2020

International audience; AgI-based Ge-Sb-S, Ga-Sb-S, and Ge-Ga-Sb-S chalcogenide glasses were designed and prepared by melt-quenching, thereafter their thermal properties and conductive performance were comparatively investigated on the basis of their composition-induced network structures. Glass transition in each sample was examined by DSC measurements. Results showed that the samples containing Ge had a higher thermal stability than the Ga-Sb-S-AgI sample, and the Ge-Sb-S-AgI sample obtained had the highest conductivity ion. Raman spectrum analysis was performed, and the results indicated that the [GeS4-xIx] structural units and [SbS3-xIx] pyramids in the matrix produced effective ion transport channel for dissolved conductive Ag+ ions. In the matrix containing Ga, the [Ga(Ge)S4-xIx] structure was consumed by part of [S3Ga-GaS3] ethane-like units, which had no contribution to the ion transition framework. The study provided the directions for composition and structure configuration control in effective conductive chalcogenide glasses.