Crystallization of a precursor Li10GeP2S12 (LGPS) glass electrolyte by heat treatment significantly improves its ionic conductivity. The LGPS crystalline phase obtained by heat treatment above 450 degrees C shows an ionic conductivity on the order of 10(-2) S/cm. To clarify the correlation between the crystallization behavior of precursor LGPS glasses and ionic conductivity, we developed an observation technique to visualize precipitated nanocrystallites and a new method to evaluate the crystallization degree via transmission electron microscopy (TEM). In-situ TEM observation revealed that LGPS nanocrystallites precipitated above 450 degrees C and their size remained fundamentally intact during heating. That is, the crystallization behavior could be characterized by only the formation of LGPS nanocrystallites in an amorphous matrix. In addition, the crystallization degree was quantitatively evaluated from electron diffraction patterns. The crystallization degree remarkably increased at around 450 degrees C and reached more than 60% above 450 degrees C. Based on these results, a high ionic conductivity of approximately 1.0 x 10(-2) S/cm was confirmed to be directly associated with the appearance of the LGPS crystalline phase. (C) 2017 Elsevier B.V. All rights reserved.