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

Zhou, Laidong; Bazak, J. David; Singh, Baltej; Li, Chang; Assoud, Abdeljalil; Washton, Nancy M.; Murugesan, Vijayakumar; Nazar, Linda F.

doi:10.1002/ange.202300404

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

Journal Article · 20 June 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202300404 · OSTI ID:1985715

^[1];

^[2]; Singh, Baltej ^[1]; Li, Chang ^[1]; Assoud, Abdeljalil ^[3];

^[2];

^[1]

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
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
Department of Chemistry and the Waterloo Institute for Nanotechnology University of Waterloo N2L 3G1 Waterloo Ontario Canada

Abstract 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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1985715

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 30 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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