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Preparation and Characterization of Cation-Substituted Na3SbS4 Solid Electrolytes

  • Fumika Tsuji
    Fumika Tsuji
    Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
    More by Fumika Tsuji
  • Naoki Masuzawa
    Naoki Masuzawa
    Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
  • Atsushi Sakuda
    Atsushi Sakuda
    Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
  • Masahiro Tatsumisago
    Masahiro Tatsumisago
    Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
  • , and 
  • Akitoshi Hayashi*
    Akitoshi Hayashi
    Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan
    Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Sakyo, Kyoto 606-8501, Japan
    *Email: [email protected]. Phone: +81-72-254-9334. Fax: +81-72-254-9910.
Cite this: ACS Appl. Energy Mater. 2020, 3, 12, 11706–11712
Publication Date (Web):December 9, 2020
https://doi.org/10.1021/acsaem.0c01823
Copyright © 2020 American Chemical Society

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    Abstract

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    To realize all-solid-state sodium-ion batteries, the ionic conductivities and stabilities of solid electrolytes must be improved. The sulfide Na3SbS4 electrolyte is known to show a high sodium-ion conductivity of over 10–3 S cm–1 at room temperature. In this study, cation-substituted Na3SbS4 solid electrolytes with excess Na or Na vacancies were prepared, and the effects of substitution on the material conductivity were examined. The ionic conductivities of the Na3+xSb1–xMxS4 (M = Si, Ge, Sn) electrolytes, which were doped with excess Na, were lower than that of the Na3SbS4 electrolyte; in contrast, the conductivities of the Na3–xSb1–xMoxS4 electrolytes, which were doped with Na vacancies, were higher. The Na2.88Sb0.88Mo0.12S4 electrolyte showed the highest room-temperature ionic conductivity of 3.9 × 10–3 S cm–1 and the lowest activation energy for conduction of 21 kJ mol–1. To improve the ionic conductivity of the Na3SbS4 electrolyte, introducing Na vacancies instead of excess Na was found to be effective.

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    • X-ray diffraction (XRD) patterns, Raman spectra, and cell parameters of the prepared materials (PDF)

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    This article is cited by 16 publications.

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    2. Theodosios Famprikis, Houssny Bouyanfif, Pieremanuele Canepa, Mohamed Zbiri, James A. Dawson, Emmanuelle Suard, François Fauth, Helen Y. Playford, Damien Dambournet, Olaf J. Borkiewicz, Matthieu Courty, Oliver Clemens, Jean-Noël Chotard, M. Saiful Islam, Christian Masquelier. Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy. Chemistry of Materials 2021, 33 (14) , 5652-5667. https://doi.org/10.1021/acs.chemmater.1c01113
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    8. Qi Liu, Xiaohan Zhao, Qiang Yang, Lijuan Hou, Daobin Mu, Guoqiang Tan, Li Li, Renjie Chen, Feng Wu. The Progress in the Electrolytes for Solid State Sodium‐Ion Battery. Advanced Materials Technologies 2023, 8 (7) https://doi.org/10.1002/admt.202200822
    9. Armand Lannerd, Karen Ly, Alevtina Smirnova. Beyond lithium: Solid-state sodium-ion batteries and their potential applications. 2023, 223-262. https://doi.org/10.1016/B978-0-323-90635-7.00009-9
    10. Matej Baláž, Martin Stahorský, Peter Baláž, Erika Dutková, Marcela Achimovičová. One-Step Solid-State Mechanochemical Synthesis of Metal Chalcogenides as a Perspecitve Alternative to Traditional Preparation Routes. 2023, 343-378. https://doi.org/10.1007/978-3-031-23401-9_12
    11. Kota MOTOHASHI, Akira NASU, Takuya KIMURA, Chie HOTEHAMA, Atsushi SAKUDA, Masahiro TATSUMISAGO, Akitoshi HAYASHI. Sodium-Ion Conducting Solid Electrolytes in the Na2S–In2S3 System. Electrochemistry 2022, 90 (6) , 067009-067009. https://doi.org/10.5796/electrochemistry.22-00037
    12. Jieren Shao, Jingfeng Zheng, Lei Qin, Songwei Zhang, Yang Ren, Yiying Wu. K 3 SbS 4 as a Potassium Superionic Conductor with Low Activation Energy for K–S Batteries. Angewandte Chemie 2022, 134 (20) https://doi.org/10.1002/ange.202200606
    13. Jieren Shao, Jingfeng Zheng, Lei Qin, Songwei Zhang, Yang Ren, Yiying Wu. K 3 SbS 4 as a Potassium Superionic Conductor with Low Activation Energy for K–S Batteries. Angewandte Chemie International Edition 2022, 61 (20) https://doi.org/10.1002/anie.202200606
    14. Randy Jalem, Bo Gao, Hong-Kang Tian, Yoshitaka Tateyama. Theoretical study on stability and ion transport property with halide doping of Na 3 SbS 4 electrolyte for all-solid-state batteries. Journal of Materials Chemistry A 2022, 10 (5) , 2235-2248. https://doi.org/10.1039/D1TA07292G
    15. Selim Halacoglu, Sabina Chertmanova, Yan Chen, Yang Li, Manthila Rajapakse, Gamini Sumanasekera, Badri Narayanan, Hui Wang. Visualization of Solid‐State Synthesis for Chalcogenide Na Superionic Conductors by in‐situ Neutron Diffraction. ChemSusChem 2021, 14 (23) , 5161-5166. https://doi.org/10.1002/cssc.202101839
    16. Roman Schlem, Christine Friederike Burmeister, Peter Michalowski, Saneyuki Ohno, Georg F. Dewald, Arno Kwade, Wolfgang G. Zeier. Energy Storage Materials for Solid‐State Batteries: Design by Mechanochemistry. Advanced Energy Materials 2021, 11 (30) , 2101022. https://doi.org/10.1002/aenm.202101022

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