We present neutron diffraction results on superionic materials that are good candidates for use as solid-state electrolytes in next generation Li+ ion batteries. Lithium ion conducting glasses of the compositions xLi2SO4-(1-x) [0.5Li2O-0.5(2NH4H2PO2)] ; x=0 and 0.1 were synthesized by conventional melt-quenching. The transparent homogeneous glassy flakes were thus obtained and used for the characterization. The materials are glassy in nature and composed of a complex network of the following sub-units: Li2O, Li2SO4, and 2NH4H2PO2. This disordered structure is integral to its function in that it promotes Li+ ion conduction while suppressing electronic conduction, the necessary qualities of a good Li+ electrolyte. We used neutron diffraction to study the formation of crystallites upon heating of the material above 400°C. The crystallite formation is understood to be detrimental to the Li+ ion mobility and, hence, is identified with a diminished performance in devices that require heating in their fabrication processs. Here, we report the changes in the material, as observed by neutron diffraction, as a function of annealing temperature and temperature history.