Analysis of structural and thermal stability in the positive electrode for sulfide-based all-solid-state lithium batteries

Sulfide-based all-solid-state batteries using a non-flammable inorganic solid electrolyte are promising candidates as a next-generation power source owing to their safety and excellent charge-discharge cycle characteristics. In this study, we thus focus on the positive electrode and investigated structural stabilities of the interface between the positive electrode active material LiNi1/3Mn1/3Co1/3O2 (NMC) and the 75Li2S·25P2S5 (LPS) glass electrolyte after charge-discharge cycles via transmission electron microscopy (TEM). To evaluate the thermal stability of the fabricated all-solid-state cell, in-situ TEM observations for the positive electrode during heating are conducted. As a result, structural and morphological changes are detected in the LPS glasses. Thus, exothermal reaction present in the NMC-LPS composite positive electrode after the initial charging is attributable to the crystallization of LPS glasses. On the basis of a comparison with crystallization behavior in single LPS glasses, the origin of exothermal reaction in the NMC-LPS composites is discussed.