A New Sodium Thioborate Fast Ion Conductor: Na 3 B 5 S 9 .

Autor: Zhou L; Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada.; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA., Bazak JD; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA.; Physical & Computational Science Directorate, Pacific Northwest National Laboratory, 99354, Richland, WA, USA., Singh B; Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada.; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA., Li C; Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada.; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA., Assoud A; Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada., Washton NM; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA.; Physical & Computational Science Directorate, Pacific Northwest National Laboratory, 99354, Richland, WA, USA., Murugesan V; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA.; Physical & Computational Science Directorate, Pacific Northwest National Laboratory, 99354, Richland, WA, USA., Nazar LF; Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada.; Joint Centre for Energy Storage Research, Argonne National Laboratory, 60439, Argonne, IL, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Jul 24; Vol. 62 (30), pp. e202300404. Date of Electronic Publication: 2023 Jun 20.
DOI: 10.1002/anie.202300404
Abstrakt: We report a new sodium fast-ion conductor, Na 3 B 5 S 9 , that exhibits a high Na ion total conductivity of 0.80 mS cm -1 (sintered pellet; cold-pressed pellet=0.21 mS cm -1 ). The structure consists of corner-sharing B 10 S 20 supertetrahedral clusters, which create a framework that supports 3D Na ion diffusion channels. The Na ions are well-distributed in the channels and form a disordered sublattice spanning five Na crystallographic sites. The combination of structural elucidation via single crystal X-ray diffraction and powder synchrotron X-ray diffraction at variable temperatures, solid-state nuclear magnetic resonance spectra and ab initio molecular dynamics simulations reveal high Na-ion mobility (predicted conductivity: 0.96 mS cm -1 ) and the nature of the 3D diffusion pathways. Notably, the Na ion sublattice orders at low temperatures, resulting in isolated Na polyhedra and thus much lower ionic conductivity. This highlights the importance of a disordered Na ion sublattice-and existence of well-connected Na ion migration pathways formed via face-sharing polyhedra-in dictating Na ion diffusion.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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