Coupled cation–anion dynamics enhances cation mobility in room-temperature superionic solid-state electrolytes

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dc.contributor.authorZhang, ZZen_AU
dc.contributor.authorRoy, PNen_AU
dc.contributor.authorLi, Hen_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorNazar, LFen_AU
dc.date.accessioned2021-01-28T05:53:41Zen_AU
dc.date.available2021-01-28T05:53:41Zen_AU
dc.date.issued2019-11-08en_AU
dc.date.statistics2021-01-12en_AU
dc.description.abstractSingle-ion conducting solid electrolytes are gaining tremendous attention as essential materials for solid-state batteries, but a comprehensive understanding of the factors that dictate high ion mobility remains elusive. Here, for the first time, we use a combination of the Maximum Entropy Method analysis of room-temperature neutron powder diffraction data, ab initio molecular dynamics, and joint-time correlation analysis to demonstrate that the dynamic response of the anion framework plays a significant role in the new class of fast ion conductors, Na11Sn2PnX12 (Pn = P, Sb; X = S, Se). Facile [PX4]3– anion rotation exists in superionic Na11Sn2PS12 and Na11Sn2PSe12, but greatly hindered [SbS4]3– rotational dynamics are observed in their less conductive analogue, Na11Sn2SbS12. Along with introducing dynamic frustration in the energy landscape, the fluctuation caused by [PX4]3– anion rotation is firmly proved to couple to and facilitate long-range cation mobility, by transiently widening the bottlenecks for Na+-ion diffusion. The combined analysis described here resolves the role of the long-debated paddle-wheel mechanism, and is the first direct evidence that anion rotation significantly enhances cation migration in rotor phases. The joint-time correlation analysis developed in our work can be broadly applied to analyze coupled cation–anion interplay where traditional transition state theory does not apply. These findings deliver important insights into the fundamentals of ion transport in solid electrolytes. Invoking anion rotational dynamics provides a vital strategy to enhance cation conductivity and serves as an additional and universal design principle for fast ion conductors. © 2019 American Chemical Societyen_AU
dc.identifier.citationZhang, Z., Roy, P.-N., Li, H., Avdeev, M., & Nazar, L. F. (2019). Coupled cation–anion dynamics enhances cation mobility in room-temperature superionic solid-state electrolytes. Journal of the American Chemical Society, 141(49), 19360–19372. doi:10.1021/jacs.9b09343en_AU
dc.identifier.issn1520-5126en_AU
dc.identifier.issue49en_AU
dc.identifier.journaltitleJournal of the American Chemical Societyen_AU
dc.identifier.pagination19360-19372en_AU
dc.identifier.urihttps://doi.org/10.1021/jacs.9b09343en_AU
dc.identifier.urihttps://apo.ansto.gov.au/dspace/handle/10238/10276en_AU
dc.identifier.volume141en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectAnionsen_AU
dc.subjectCationsen_AU
dc.subjectLigandsen_AU
dc.subjectDiffusionen_AU
dc.subjectMolecular dynamics methoden_AU
dc.subjectEntropyen_AU
dc.subjectSolid electrolytesen_AU
dc.subjectElectric batteriesen_AU
dc.titleCoupled cation–anion dynamics enhances cation mobility in room-temperature superionic solid-state electrolytesen_AU
dc.typeJournal Articleen_AU
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