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Superionic Ag+ Conductor Ag17(CO3)3I11

  • Yuta Watanabe
    Yuta Watanabe
    Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
  • Ryoji Suzuki
    Ryoji Suzuki
    Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
    More by Ryoji Suzuki
  • Kazuto Kato
    Kazuto Kato
    Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
    More by Kazuto Kato
  • Hisanori Yamane
    Hisanori Yamane
    Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai-shi, Miyagi 980-8577, Japan
  • Mamoru Kitaura
    Mamoru Kitaura
    Faculty of Science, Yamagata University, 1-4-12 Kojirakawamachi, Yamagata-shi, Yamagata 990-8560, Japan
  • Toshiaki Ina
    Toshiaki Ina
    JASRI/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
    More by Toshiaki Ina
  • Kento Uchida
    Kento Uchida
    Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
    More by Kento Uchida
  • , and 
  • Yuta Matsushima*
    Yuta Matsushima
    Chemistry and Chemical Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
    *Email: [email protected]
Cite this: Inorg. Chem. 2021, 60, 5, 2931–2938
Publication Date (Web):February 10, 2021
https://doi.org/10.1021/acs.inorgchem.0c02850
Copyright © 2021 American Chemical Society

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    Abstract

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    A new superionic Ag+ conductor with a nominal composition Ag17(CO3)3I11 (11AgI–3Ag2CO3) was found in the AgI–Ag2CO3 system. The conductor, which was formed at temperatures from 100 to 170 °C, is a metastable phase that gradually decomposes into AgI and Ag10(CO3)I4 over a period of a few weeks at room temperature (RT). A Ag+ ionic conductivity of 0.16 S/cm was measured at RT, and an activation energy of 0.33 eV was evaluated in the temperature range from −9 to 19 °C. Single-crystal X-ray analysis revealed that Ag17(CO3)3I11 crystallized in a rhombohedral unit cell with hexagonal parameters of a = 15.8831(6) Å and c = 30.0730(13) Å at −183 °C and space group R3c. The Ag atoms were distributed over 53 sites in the asymmetry unit, with a maximum occupancy of 0.33(8). The continuous distribution of the partially occupied Ag sites was associated with the conduction paths of the Ag+ ions in the structure.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02850.

    • Crystal data and refinement results of single-crystal XRD, supporting powder XRD patterns, crystal structure illustrating statistical model, and supporting Cole–Cole plots (PDF)

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    CCDC 2033736 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 2 publications.

    1. Kento Uchida, Yuta Matsushima. Investigation of AgI-Based Solid Solutions with Ag2CO3. Technologies 2021, 9 (3) , 54. https://doi.org/10.3390/technologies9030054
    2. Ryoji Suzuki, Yuta Watanabe, Hisanori Yamane, Mamoru Kitaura, Kento Uchida, Yuta Matsushima. Crystal structure of silver carbonate iodide Ag 10 (CO 3 ) 3 I 4. Acta Crystallographica Section E Crystallographic Communications 2021, 77 (7) , 734-738. https://doi.org/10.1107/S2056989021006022

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