# Activation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study https://mdr.nims.go.jp/datasets/b37d5389-80e6-4fc8-b490-ce0634706ff9 ## File - [shinoda-et-al-2025-activation-of-anionic-redox-for-stoichiometric-and-li-excess-metal-sulfides-through-structural.pdf](https://mdr.nims.go.jp/filesets/1aae0091-e122-48cd-ac28-01585443447b/download) ([Detail](https://mdr.nims.go.jp/filesets/1aae0091-e122-48cd-ac28-01585443447b.md)) ## Id b37d5389-80e6-4fc8-b490-ce0634706ff9 ## Local identifier ## Visibility open_to_public ## State published ## Created at 2025-07-31T02:03:04.477559Z ## Updated at 2025-07-31T07:30:23.019765Z ## Published at 2025-07-31T07:17:50.387255Z ## Doi ## First published url https://doi.org/10.1021/jacs.5c04018 ## Date published 2025-07-30 ## Recorded date published 2025-7-30 ## Resource type journal_article ## Manuscript type vor ## Collection ## Title - title: 'Activation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study' title_type: original lang: en ## Description - description: 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 that a unique local structure for a sulfide ion coordinated by 6 Li ions, SLi6 configuration, is formed, which can be found only for the disordered structure and not for the layered structure. The unique local structure triggers electron delocalization for sulfide 3p orbitals, leading to superior electronic conductivity, as experimentally evidenced, and thus anionic redox is successfully activated. Furthermore, such nonuniform local structures lead to easier structural distortion and efficient S–S dimerization, and even trimerization (S32–), upon delithiation. Although sulfide-based compounds as battery electrode materials suffer from dissolution after oxidation, this practical problem is effectively mitigated by the use of highly concentrated electrolyte solutions with fewer free solvent molecules, leading to superior reversibility for anionic redox. The insights derived can guide the development of high-energy electrode materials with anionic redox with or without transition metal ions possessing conductive d electrons. description_type: abstract lang: und ## Creator - name: Miyuki Shinoda role: author - name: Koki Matsunoshita role: author - name: Masanobu Nakayama role: author orcid: https://orcid.org/0000-0002-5113-053X - name: Satoshi Hiroi role: author orcid: https://orcid.org/0000-0001-5058-6757 - name: Koji Ohara role: author - name: Masaki Abe role: author orcid: https://orcid.org/0009-0002-1369-629X - name: Nozomu Ishiguro role: author orcid: https://orcid.org/0000-0003-3330-6236 - name: Yukio Takahashi role: author - name: Gen Hasegawa role: author orcid: https://orcid.org/0000-0002-9297-6902 - name: Naoaki Kuwata role: author orcid: https://orcid.org/0000-0002-0736-6967 - name: Tsukasa Iwama role: author orcid: https://orcid.org/0000-0002-1453-6936 - name: Takuya Masuda role: author orcid: https://orcid.org/0000-0001-7462-2177 - name: Kosuke Suzuki role: author - name: Hirofumi Ishii role: author - name: Yu-Cheng Shao role: author - name: Daisuke Shibata role: author - name: Akinori Irizawa role: author - name: Toshiaki Ohta role: author - name: Itsuki Konuma role: author - name: Teppei Ohno role: author - name: Yosuke Ugata role: author orcid: https://orcid.org/0000-0002-8233-6725 - name: Naoaki Yabuuchi role: author orcid: https://orcid.org/0000-0002-9404-5693 ## Contact agent ## Publisher organization: American Chemical Society (ACS) ## Managing organization ## Keyword - subject: Li-ion battery schema: not_defined - subject: High-capacity positive electrode schema: not_defined - subject: Anionic redox schema: not_defined - subject: Sulfides schema: not_defined - subject: Transition metals schema: not_defined ## Rights - identifier: https://creativecommons.org/licenses/by/4.0/ ## Other identifier(s) ## Data origin - data_origin_type: other ## Embargo ## Journal - title: Journal of the American Chemical Society issn: '00027863' volume: '147' issue: '30' start_page: 26238 end_page: 26253 ## Conference ## Related item ## Funding - identifier: JPMJGX23S3 funder_name: Japan Science and Technology Agency - identifier: JPMJGX23S5 funder_name: Japan Science and Technology Agency - identifier: JPMJPF2016 funder_name: Japan Science and Technology Agency - identifier: JPMXP1122712807 funder_name: Ministry of Education, Culture, Sports, Science and Technology - identifier: 19H05814 funder_name: Japan Society for the Promotion of Science - identifier: 21H04698 funder_name: Japan Society for the Promotion of Science - identifier: 24H02204 funder_name: Japan Society for the Promotion of Science - identifier: JPMJAP2313 funder_name: Japan Science and Technology Agency - identifier: JPMJCR21O6 funder_name: Japan Science and Technology Agency ## Instrument ## Instrument operator ## Instrument managing organization ## Measurement method ## Specimen ## Chemical composition ## Structure for specimen ## Structural feature for specimen ## Specific property for specimen ## Process for specimen treatment ## Computational method ## Energy level/transition state ## Software ## Custom property ## Fileset - id: 1aae0091-e122-48cd-ac28-01585443447b filename: shinoda-et-al-2025-activation-of-anionic-redox-for-stoichiometric-and-li-excess-metal-sulfides-through-structural.pdf content_type: application/pdf size: 8720861 md5: dd4b65fd3ebb56e08757fcb574a62336 ## Thumbnail fileset_id: 1aae0091-e122-48cd-ac28-01585443447b filename: shinoda-et-al-2025-activation-of-anionic-redox-for-stoichiometric-and-li-excess-metal-sulfides-through-structural.pdf