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An Insight into Sodiation of Antimony from First-Principles Crystal Structure Prediction

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Abstract

Elemental antimony has recently become an attractive anode material for potential application in rechargeable sodium-ion batteries. I present a first-principles study of the structure–composition dependence of the Na–Sb system for both sodiation and desodiation processes. The enthalpy of reaction of x moles of sodium with the hexagonal structure of antimony reveals several stable crystal structures for 0 < x ≤ 3, with variable composition states for 1.25 < x < 2.75. The direct and reverse reactions pass through similar states in terms of enthalpy of formation and symmetry representation of the corresponding optimized structures, in particular for x = 1 and x = 3, confirming the two known phases, namely NaSb and Na3Sb. The calculations suggest that the optimal composition range for reversible sodiation of antimony is 1 < x ≤ 3, thus avoiding the global minimum at x = 1. This can help to rationalize the structure–composition dependence of the electrochemical performance of antimony in Na-ion batteries.

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Authors and Affiliations

  1. Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland

    Riccarda Caputo

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  1. Riccarda Caputo
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Correspondence to Riccarda Caputo.

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Caputo, R. An Insight into Sodiation of Antimony from First-Principles Crystal Structure Prediction. J. Electron. Mater. 45, 999–1010 (2016). https://doi.org/10.1007/s11664-015-4260-0

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