Effect of Li2SO4 on the properties of Li2S-P2S5 glass-ceramic solid electrolytes

Glass-ceramic solid electrolytes of (100-x)(78Li(2)S center dot 22P(2)S(5))center dot xLi(2)SO(4) (x=0, 4, and 5) were prepared by high-energy mechanical milling and subsequent heat-treatment. The low thermal stability of the metastable thio-LISICON II analog phase of the 78Li(2)S center dot 22P(2)S(5) glass-ceramics was identified by gradual transformation to a thio-LISICON III analog phase over a narrow temperature range of heat treatment. However, the addition of 5 mol% Li2SO4 into the 78Li(2)S center dot 22P(2)S(5) glass-ceramics suppressed the formation of the thio-LISICON DI analog phase and enhanced the structural stability of the thio-LISICON II analog phase at higher heat treatment temperatures. From X-ray diffraction (XRD) and differential thermal analysis (DTA) results, the enhanced thermal stability of the thio-LISICON II analog phase in the Li2SO4 added 78Li(2)S center dot 22P(2)S(5) glass-ceramics is closely related to the lithium content of the glass matrix and the incorporated tetrahedral SO42- anions in the crystal lattice of the thio-LISICON II analog phase. (c) 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.