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Vacancy‐Controlled Na+ Superion Conduction in Na11Sn2PS12

Duchardt, Marc ; Ruschewitz, Uwe ; Adams, Stefan ; Dehnen, Stefanie ; Roling, Bernhard

Angewandte Chemie International Edition, 2018-01, Vol.57 (5), p.1351-1355 [Periódico revisado por pares]

Weinheim: Wiley Subscription Services, Inc

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  • Título:
    Vacancy‐Controlled Na+ Superion Conduction in Na11Sn2PS12
  • Autor: Duchardt, Marc ; Ruschewitz, Uwe ; Adams, Stefan ; Dehnen, Stefanie ; Roling, Bernhard
  • Assuntos: Batteries ; BVSE calculations ; Conduction ; Conductivity ; Conductors ; Diffraction ; Electrolytes ; Ions ; Lithium ; Molten salt electrolytes ; powder X-ray diffraction ; preexponential factor ; Sodium ; sodium-ion conductor ; Solid electrolytes ; Sulfide ; superionic conductivity ; Vacancies ; X ray powder diffraction
  • É parte de: Angewandte Chemie International Edition, 2018-01, Vol.57 (5), p.1351-1355
  • Descrição: Highly conductive solid electrolytes are crucial to the development of efficient all‐solid‐state batteries. Meanwhile, the ion conductivities of lithium solid electrolytes match those of liquid electrolytes used in commercial Li+ ion batteries. However, concerns about the future availability and the price of lithium made Na+ ion conductors come into the spotlight in recent years. Here we present the superionic conductor Na11Sn2PS12, which possesses a room temperature Na+ conductivity close to 4 mS cm−1, thus the highest value known to date for sulfide‐based solids. Structure determination based on synchrotron X‐ray powder diffraction data proves the existence of Na+ vacancies. As confirmed by bond valence site energy calculations, the vacancies interconnect ion migration pathways in a 3D manner, hence enabling high Na+ conductivity. The results indicate that sodium electrolytes are about to equal the performance of their lithium counterparts. Solid electrolyte: Na11Sn2PS12 was synthesized from Na3PS4 and Na4SnS4 and turned out to be the best sulfide‐based Na+ conductor known to date. With 3.7 mS cm−1, its performance is in the range of related Li+ superion conductors, although the composition and crystal structures are different. The high ionic conductivity was explained with the help of bond valence site energy calculations.
  • Editor: Weinheim: Wiley Subscription Services, Inc
  • Idioma: Inglês
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