Dimer-mediated cooperative mechanism of ultrafast-ion conduction in hexagonal perovskite-related oxides

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dc.contributor.authorSakuda, Yen_AU
dc.contributor.authorMurakami, Ten_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorFujii, Ken_AU
dc.contributor.authorYasui, Yen_AU
dc.contributor.authorHester, JRen_AU
dc.contributor.authorHagihala, Men_AU
dc.contributor.authorIkeda, Yen_AU
dc.contributor.authorNambu, Yen_AU
dc.contributor.authorYashima, Men_AU
dc.date.accessioned2024-12-06T03:30:47Zen_AU
dc.date.available2024-12-06T03:30:47Zen_AU
dc.date.issued2023-11-14en_AU
dc.date.statistics2024-06-06en_AU
dc.description.abstractOxide-ion and proton conductors have found diverse applications such as in electrolytes of solid-oxide, proton-conducting, and hybrid-ion fuel cells. Research of fuel cells with higher energy efficiency at lower operating temperature has stimulated the search for ion conductors and improved the understanding of the ion-diffusion mechanism. Ion conduction in hexagonal perovskite-related materials is rare, and the mechanism of ion diffusion is unclear. Herein, we report high oxide-ion and proton conductivity (bulk conductivities in wet air: 11 and 2.7 mS cm-1 at 537 and 326 °C, respectively), high chemical, and electrical stability in a new hexagonal perovskite-related oxide Ba7Nb3.8Mo1.2O20.1. Total direct current conductivity at 400 °C in wet air of Ba7Nb3.8Mo1.2O20.1 was 13 times higher than that of Ba7Nb4MoO20. We also report a unique dimer-mediated cooperative mechanism of the high oxide-ion conduction of Ba7Nb3.8Mo1.2O20.1 (bulk conductivities in dry air: 10 mS cm-1 at 593 °C and 1.1 mS cm-1 at 306 °C). Ab initio molecular dynamics (AIMD) simulations, neutron-diffraction experiments at 800 °C, and neutron scattering length density analyses of Ba7Nb3.8Mo1.2O20.1 indicated that the excess oxygen atoms are incorporated by the formation of both 5-fold coordinated (Nb/Mo)O5 monomer and its (Nb/Mo)2O9 dimer with a corner-sharing oxygen atom and that the breaking and reforming of the dimers lead to the high oxide-ion conduction in the oxygen-deficient BaO2.1 c′ layer. The long distance between Nb/Mo and Ba cations sandwiching the c′ layer of Ba7Nb3.8Mo1.2O20.1 was found to be responsible for its low activation energy for oxide-ion conduction, leading to high conductivity at low temperatures. AIMD simulations showed that high proton conduction can be attributed to proton migration in the hexagonal close-packed BaO3 layers of Ba7Nb3.8Mo1.2O20.1. The present findings hold a great promise for the development and design of ion conductors. Copyright © 2023 The Authors. Published by American Chemical Society.en_AU
dc.description.sponsorshipThis study was partly supported by Grants-in-Aid for Scientific Research (KAKENHI, JP19H00821, JP19K23647, JP21K14701, JP21K18182, JP22H04504, JP23K04887, JP23H04618, JP21H03732, JP22H05145) from the Ministry of Education, Culture, Sports, Science and Technology of Japan, Adaptable and Seamless Technology Transfer Program through Target-driven R&D (A-STEP) from the Japan Science and Technology Agency (JST) Grant Number JPMJTR22TC, JST FOREST (Grant No. JPMJFR202V), and JSPS Core-to-Core Program, A. Advanced Research Networks (Solid Oxide Interfaces for Faster Ion Transport, and Mixed Anion Research for Energy Conversion [JPJSCCA20200004]). Y.S. and Y.Y. were supported by JSPS Research Fellowships for Young Scientists DC1 (21J22818 and 20J23124). M.A. expresses thanks for the support from JSPS (Invitational Fellowships for Research in Japan L19533). T.M. acknowledges support from the Izumi Science and Technology Foundation, the Iwatani Naoji Foundation, the Daiichi Kigenso Kagaku Kogyo Co., Ltd., the Hattori Hokokai Foundation, and Iketani Science and Technology.en_AU
dc.identifier.citationSakuda, Y., Murakami, T., Avdeev, M., Fujii, K., Yasui, Y., Hester, J. R., Hagihala, M., Ikeda, Y., Nambu, Y., & Yashima, M. (2023). Dimer-mediated cooperative mechanism of ultrafast-ion conduction in hexagonal perovskite-related oxides. Chemistry of Materials, 35(22), 9774-9788. doi:10.1021/acs.chemmater.3c02378en_AU
dc.identifier.issn0897-4756en_AU
dc.identifier.issn1520-5002en_AU
dc.identifier.issue22en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination9774-9788en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.chemmater.3c02378en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/15806en_AU
dc.identifier.volume35en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectOxidesen_AU
dc.subjectPerovskiteen_AU
dc.subjectElectrolytesen_AU
dc.subjectProton conductivityen_AU
dc.subjectDiffusionen_AU
dc.subjectTemperature rangeen_AU
dc.subjectElectric conductivityen_AU
dc.subjectAtmospheric chemistryen_AU
dc.subjectOxygenen_AU
dc.subjectScatteringen_AU
dc.subjectEnergyen_AU
dc.titleDimer-mediated cooperative mechanism of ultrafast-ion conduction in hexagonal perovskite-related oxidesen_AU
dc.typeJournal Articleen_AU
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