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oai:ynu.repo.nii.ac.jp:02001985 2025-08-27T00:53:10Z 1006:1009 495:496

Activation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study Shinoda, Miyuki Yokohama National University 横浜国立大学 Matsunoshita, Koki Nagoya Institute of Technology 0000-0002-5113-053X Nakayama, Masanobu Nagoya Institute of Technology 0000-0001-5058-6757 Hiroi, Satoshi Shimane University Ohara, Koji Shimane University RIKEN 0009-0002-1369-629X Abe, Masaki RIKEN Tohoku University 0000-0003-3330-6236 Ishiguro, Nozomu RIKEN Tohoku University Takahashi, Yukio RIKEN Tohoku University 0000-0002-9297-6902 Hasegawa, Gen National Institute for Materials Science 0000-0002-0736-6967 Kuwata, Naoaki National Institute for Materials Science Iwama, Tsukasa National Institute for Materials Science Hokkaido University 0000-0001-7462-2177 Masuda, Takuya National Institute for Materials Science Hokkaido University Suzuki, Kosuke Gunma University Ishii, Hirofumi National Synchrotron Radiation Research Center Shao, Yu-Cheng National Synchrotron Radiation Research Center Shibata, Daisuke Ritsumeikan University Irizawa, Akinori Ritsumeikan University Ohta, Toshiaki Ritsumeikan University Konuma, Itsuki Yokohama National University 横浜国立大学 Ohno, Teppei Yokohama National University 横浜国立大学 0000-0002-8233-6725 Ugata, Yosuke Yokohama National University 横浜国立大学 80529488 0000-0002-9404-5693 Yabuuchi, Naoaki Yokohama National University 横浜国立大学 open access Creative Commons Attribution 4.0 International Chemical structure Electrodes Ions Sulfides Transition metals 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. American Chemical Society 2025-07-15 eng journal article VoR http://hdl.handle.net/10131/0002001985 https://ynu.repo.nii.ac.jp/records/2001985 https://doi.org/10.1021/jacs.5c04018 1025 Japan Society for the Promotoion of Science 独立行政法人日本学術振興会 JP21H04698 アニオンレドックスの可逆性を支配する原理解明と革新的蓄電池材料設計への応用 1025 Japan Society for the Promotoion of Science 独立行政法人日本学術振興会 JP24H02204 イオン渋滞学に基づく新物質創製と機能開拓 1020 Japan Science and Technology Agency 国立研究開発法人科学技術振興機構 JPMJCR21O6 水を基軸とする未踏蓄電機能材料の開拓 1001 Ministry of Education 文部科学省 JPMXP1122712807 再生可能エネルギー最大導入に向けた電気化学材料研究拠点(DX-GEM) 1020 Japan Science and Technology Agency 国立研究開発法人科学技術振興機構 JPMJAP2313 分散型国際ネットワークが実現する基盤蓄電技術革新とネットゼロ社会 1020 Japan Science and Technology Agency 国立研究開発法人科学技術振興機構 JPMJPF2016 先進蓄電池研究開発拠点 1025 Japan Society for the Promotoion of Science 独立行政法人日本学術振興会 JP19H05814 高度計測の統合利用による蓄電固体界面の物理化学局所状態の解明 1020 Japan Science and Technology Agency 国立研究開発法人科学技術振興機構 JPMJGX23S3 高エネルギー密度を有する高温作動長寿命リチウム系電池の開発 1020 Japan Science and Technology Agency 国立研究開発法人科学技術振興機構 JPMJGX23S5 高エネルギー密度・高安全な硫化物型全固体電池の開発 01xjv7358 Japan Synchrotron Radiation Research Institute 公益財団法人高輝度光科学研究センター 2023A1001 01xjv7358 Japan Synchrotron Radiation Research Institute 公益財団法人高輝度光科学研究センター 2023G028 01xjv7358 Japan Synchrotron Radiation Research Institute 公益財団法人高輝度光科学研究センター 2021B1595 1520-5126 0002-7863 Journal of the American Chemical Society 147 30 16 26238 26253 https://ynu.repo.nii.ac.jp/record/2001985/files/shinoda-et-al-2025-activation-of-anionic-redox-for-stoichiometric-and-li-excess-metal-sulfides-through-structural.pdf application/pdf 8.3 MB 2025-08-02