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Hydride-ion-conducting K2NiF4-type Ba–Li oxyhydride solid electrolyte

Nature Materials volume 21, pages 325–330 (2022)Cite this article

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Abstract

Hydrogen transport in solids, applied in electrochemical devices such as fuel cells and electrolysis cells, is key to sustainable energy societies. Although using proton (H+) conductors is an attractive choice, practical conductivity at intermediate temperatures (200–400 °C), which would be ideal for most energy and chemical conversion applications, remains a challenge. Alternatively, hydride ions (H–), that is, monovalent anions with high polarizability, can be considered a promising charge carrier that facilitates fast ionic conduction in solids. Here, we report a K2NiF4-type Ba–Li oxyhydride with an appreciable amount of hydrogen vacancies that presents long-range order at room temperature. Increasing the temperature results in the disappearance of the vacancy ordering, triggering a high and essentially temperature-independent H– conductivity of more than 0.01 S cm–1 above 315 °C. Such a remarkable H– conducting nature at intermediate temperatures is anticipated to be important for energy and chemical conversion devices.

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Fig. 1: Crystal structures of as-synthesized K2NiF4-type oxyhydrides at room temperature.
Fig. 2: Structural phase transition of Ba1.75LiH2.7O0.9 prepared by ambient-pressure synthesis.
Fig. 3: Hydride conductivity of Ba1.75LiH2.7O0.9.
Fig. 4: Molecular-level H– dynamics.
Fig. 5: Comparison of H– conductivities of Ba1.75LiH2.7O0.9 and other materials.

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The data presented in the current study are available from the corresponding author on reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Precursory Research for Embryonic Science and Technology programme of the Japan Science and Technology Agency, no. JPMJPR1295 (G.K.); Grants-in-Aid nos 15H05497 (G.K.), 17H05492 (G.K.), 17H06145 (R.K.), 18H05516 (G.K.), 18H05518 (T.O.), 19H04710 (F.T.) and 20H02828 (G.K.) from the Japan Society for the Promotion of Science; and the Advanced Research Program for Energy and Environment Technologies from the New Energy and Industrial Technology Development Organization, no. 16823906 (R.K.). Synchrotron and neutron radiation experiments were approved by the Japan Synchrotron Radiation Research Institute (2016A1673, 2016B1767 and 2018B1099), the Neutron Scattering Program Advisory Committee of the Institute of Materials Structure Science, the High Energy Accelerator Research Organization (2014S06, 2014S10 and 2019S10) and the Institut Laue-Langevin (http://doi.ill.fr/10.5291/ILL-DATA.7-03-144). Electrochemical impedance spectroscopy measurements were supported by N. Higuchi (Toyo Corporation). The authors thank T. Yamamoto and T. Broux for their helpful suggestions regarding structural refinement. D.B. acknowledges the NanoSciences Programme of the Atomic Energy Commission (CEA, France) and the EU/CEA Enhanced Eurotalents Fellowship for financial support.

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Author notes

  1. These authors contributed equally: Fumitaka Takeiri, Akihiro Watanabe.

Authors and Affiliations

  1. Department of Materials Molecular Science, Institute for Molecular Science, Okazaki, Japan

    Fumitaka Takeiri, Akihiro Watanabe, Kei Okamoto, Asad Ali, Yumiko Imai, Masako Nishikawa & Genki Kobayashi

  2. The Graduate University for Advanced Studies, SOKENDAI, Hayama, Japan

    Fumitaka Takeiri, Kei Okamoto, Asad Ali, Masao Yonemura, Takashi Saito, Kazutaka Ikeda, Toshiya Otomo, Takashi Kamiyama & Genki Kobayashi

  3. Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Midori, Japan

    Akihiro Watanabe & Ryoji Kanno

  4. Université Grenoble Alpes, CEA, CNRS, IRIG, SyMMES, Grenoble, France

    Dominic Bresser & Sandrine Lyonnard

  5. Helmholtz Institute Ulm, Ulm, Germany

    Dominic Bresser

  6. Karlsruhe Institute of Technology, Karlsruhe, Germany

    Dominic Bresser

  7. Institut Laue-Langevin (ILL), Grenoble, France

    Bernhard Frick

  8. Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Ibaraki, Japan

    Masao Yonemura, Takashi Saito, Kazutaka Ikeda, Toshiya Otomo & Takashi Kamiyama

  9. Research Center for All-Solid-State Battery, Institute of Innovative Research, Tokyo Institute of Technology, Yokohama, Japan

    Ryoji Kanno

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Contributions

G.K. conceived, supervised and designed the whole study. A.W., Y.I. and M.N. synthesized the material. F.T., A.W., K.O. and Y.I. carried out the electrochemical measurements. F.T., A.W., A.A., M.Y., T.S., K.I., T.O., T.K. and G.K. collected and refined the powder SXRD and ND data. D.B., S.L., B.F. and G.K. conducted the neutron quasi-elastic measurements and analysis. All authors discussed the results; F.T. and G.K. wrote the manuscript with discussions mainly with S.L., D.B., B.F. and R.K.

Corresponding author

Correspondence to Genki Kobayashi.

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Nature Materials thanks John Irvine and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–14, Discussions 1–4 and Tables 1–4.

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Takeiri, F., Watanabe, A., Okamoto, K. et al. Hydride-ion-conducting K2NiF4-type Ba–Li oxyhydride solid electrolyte. Nat. Mater. 21, 325–330 (2022). https://doi.org/10.1038/s41563-021-01175-0

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