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Tracking Sodium-Antimonide Phase Transformations in Sodium-Ion Anodes: Insights from Operando Pair Distribution Function Analysis and Solid-State NMR Spectroscopy

Research output: Contribution to journalJournal article

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  • Phoebe K. Allan
  • John M. Griffin
  • Ali Darwiche
  • Olaf J. Borkiewicz
  • Kamila M. Wiaderek
  • Karena W. Chapman
  • Andrew J. Morris
  • Peter J. Chupas
  • Laure Monconduit
  • Clare P. Grey
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<mark>Journal publication date</mark>24/02/2016
<mark>Journal</mark>Journal of the American Chemical Society
Issue number7
Volume138
Number of pages14
Pages (from-to)2352-2365
<mark>State</mark>Published
Early online date29/01/16
<mark>Original language</mark>English

Abstract

Operando pair distribution function (PDF) analysis and ex situ Na-23 magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy are used to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline NaxSb phases from the total PDF, an approach constrained by chemical phase information gained from Na-23 ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electro-chemically; a-Na3-xSb (x approximate to 0.4-0.5), a structure locally similar to crystalline Na3Sb (c-Na3Sb) but with significant numbers of sodium vacancies and a limited correlation length, and a-Na1.7Sb, a highly amorphous structure featuring some Sb-Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na3-xSb and, finally, crystalline Na3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphofis network reacts at higher voltages reforming a-Na1.7Sb, then a-Na3-xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na3-xSb without the formation of a-Na3-xSb. a-Na3-xSb is converted to crystalline Na3Sb at the end of the second discharge. We find no evidence of formation of NaSb. Variable temperature Na-23 NMR experiments reveal significant sodium mobility within c-Na3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.