Roles of Polymerized Anionic Clusters Stimulating for Hydrolysis Deterioration in Li7P3S11

• Published in: Journal of physical chemistry. C 2021-09, Vol.125 (35), p.19509-19516
• Main Authors: Kim, Ji-Su, Jung, Wo Dum, Shin, Sung Soo, Yang, Sungeun, Park, Sangbaek, Lee, Jong-Ho, Kim, Byung-Kook, Lee, Jong-Heun, Kim, Hyoungchul
• Format: Article
• Language: English
• Subjects: C: Physical Properties of Materials and Interfaces
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.1c05034

The atmospheric hydrolysis reaction in sulfide solid electrolytes (SEs) is destructive to their Li-ion conducting behavior, but a comprehensive understanding of their reaction steps is still lacking. Therefore, here, we studied the atmospheric deterioration of a well-known sulfide SE, Li7P3S11, based on the analogies between the hydrolysis and electrochemical reactions. Through analyzing the change in the S2 p binding energy, we found that the anionic structures of both air-exposed and delithiated sulfides were altered owing to Li-ion loss. Considering the high diffusivity and massive hydrate formation ability of Li ions, we found that the anionic structures of both air-exposed and delithiated sulfides were altered. We showed that the hydrolysis of sulfide SEs with anionic polymerization has a thermodynamically favorable final state energy of −3.85 eV because S ions offer high degrees of freedom in their charge states ranging from −0.89 to −0.31e.