biostudies-literatureShinoda MMinistry of Education, Culture, Sports, Science and TechnologyJapan Science and Technology AgencyJapan Society for the Promotion of Science26238-26253https://www.ebi.ac.uk/biostudies/studies/S-EPMC12314909biostudies-literatureUnknown147(30)Extensive research efforts have been dedicated to Li-excess compounds with anionic redox reaction as potential high-capacity positive electrode materials for Li-ion battery applications. The origin of activation on anionic redox is still under debate, and a unified understanding is necessary, especially for sulfide-based compounds without conductive d electrons. Herein, joint experimental and theoretical study is conducted for Li-excess and stoichiometric compounds with different crystal structures, cation-disordered rocksalt, and cation-ordered layered structures. In contrast to the understanding of Li-excess oxides, sulfide-based compounds with ordered layered structures are electrochemically less active compared with the materials with disordered structure. Theoretical study reveals thaJournal of the American Chemical SocietyActivation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study.PMC1231490919H05814JPMJPF2016JPMJGX23S324H02204JPMXP1122712807JPMJGX23S5JPMJAP2313JPMJCR21O621H04698Shao YCKuwata NShibata DOhta TIshiguro NShinoda MIrizawa AIshii HSuzuki KKonuma ITakahashi YOhara KHasegawa GOhno TAbe MMasuda TUgata YYabuuchi NHiroi SMatsunoshita KIwama TNakayama MfalseActivation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study.Extensive research efforts have been dedicated to Li-excess compounds with anionic redox reaction as potential high-capacity positive electrode materials for Li-ion battery applications. The origin of activation on anionic redox is still under debate, and a unified understanding is necessary, especially for sulfide-based compounds without conductive d electrons. Herein, joint experimental and theoretical study is conducted for Li-excess and stoichiometric compounds with different crystal structures, cation-disordered rocksalt, and cation-ordered layered structures. In contrast to the understanding of Li-excess oxides, sulfide-based compounds with ordered layered structures are electrochemically less active compared with the materials with disordered structure. Theoretical study reveals tha2025-01-01T00:00:00Z2025 Jul2026-03-15T23:45:20.765Z2025-08-14T03:05:13.969ZS-EPMC123149094066371010.1021/jacs.5c04018