Ionothermal Synthesis of Sodium-Based Fluorophosphate Cathode Materials

  • Recham N
  • Chotard J
  • Dupont L
 et al. 
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Abstract

Owing to cost and abundance considerations, Na-based electrode materials are regaining interest, especially those that can be prepared at low temperatures. Here, we report the low temperature synthesis of highly divided Na-based fluorophosphates (Na(2)MPO(4)F, M = Fe, Mn, or mixtures) in ionic liquid media. We show that this ionothermal approach enables the synthesis of these phases at temperatures as low as 270 degrees C, while temperatures as high as 600 degrees C are needed to obtain similar quality phases by solid-state reactions. Moreover, owing to their highly divided character, Na(2)FePO(4)F powders made via such a process show better electrochemical performances vs either Li or Na than their ceramic counterparts. In contrast, regardless of how they were made, the Na(2)MnPO(4)F powders, which crystallize in a three-dimensional (3D) tunnel structure rather than in the two-dimensional (2D)-layered structure of Na(2)FePO(4)F, were poorly electroactive. Substituting 0.25 Fe for Mn in Na(2)Fe(1-x)Mn(x)PO(4)F is sufficient to trigger a 2D-3D structural transition and leads to a rapid decay of the materials electrochemical performances. A tentative explanation, based on structural considerations to account for such behavior, is given in this paper. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3236480] All rights reserved.

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Authors

  • N. Recham

  • J-N. Chotard

  • L. Dupont

  • K. Djellab

  • M. Armand

  • J-M. Tarascon

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