Effects of LiPON Incorporation on the Structures and Properties of Mixed Oxy-Sulfide-Nitride Glassy Solid Electrolytes

Glassy solid electrolytes (GSEs) are promising solid electrolytes in the development of all solid-state batteries. Mixed oxy-sulfide nitride (MOSN) GSEs combine the high ionic conductivity of sulfide glasses, the excellent chemical stability of oxide glasses, and the electrochemical stability of nitride glasses. However, the reports on the synthesis and characterization of these novel nitrogen containing electrolytes are quite limited. Therefore, the systematic incorporation of LiPON during glass synthesis was used to explore the effects of nitrogen and oxygen additions on the atomic-level structures in the glass transition (T g) and crystallization temperature (T c) of MOSN GSEs. The MOSN GSE series 58.3Li2S + 31.7SiS2 + 10­[(1 – x)­Li0.67PO2.83 + x LiPO2.53N0.314], x = 0.0, 0.06, 0.12, 0.2, 0.27, 0.36, was prepared by melt-quench synthesis. Differential scanning calorimetry was used to determine the T g and T c values of these glasses. Fourier transformation-infrared, Raman, and magic angle spinning nuclear magnetic resonance spectroscopies were used to examine the short-range order structures of these materials. X-ray photoelectron spectroscopy was conducted on the glasses to further understand the bonding environments of the doped nitrogen. Finally, N and S elemental analyses were used to confirm the composition of these GSEs. These results are used to elucidate the structure of these glasses and to understand the thermal property impact oxygen and nitrogen doping in these GSEs.