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Electrochemical Reactivity of Li2VOSiO4 toward Li

Abstract : We report on the chemical/electrochemical reactivity of the insulating layered V-based silicate-phase Li2VOSiO4 toward Li. The silicate phase, made by a ceramic approach and consisting of 5−20 μm agglomerates, exhibits only a slight reactivity with Li in chemical or electrochemical reactions. By ball milling Li2VOSiO4 in the presence of carbon, we succeeded in preparing composites that reversibly react with 0.7 Li+ per unit formula at an average voltage of 3.6 V vs Li+/Li0. This electrochemical reactivity was chemically mimicked using NO2BF4 or Br2 and LiI as oxidizing and reducing agents, respectively. Through a combination of X-rays and HRTEM measurements, we showed that the insertion−deinsertion mechanism is a two-phase process with poor kinetics. The delithiated phase crystallizes in space group P4 (a = 6.206 Å, c = 4.5715Å), whereas the precursor lithiated phase crystallizes in P4/nmm (a = 6.366(9) Å, c = 4.456(6) Å). Because silicates such as phosphates are cheap and can also be made redox-active by carbon coatings, they should not be overlooked as possible electrode candidates in future research.
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Soumis le : jeudi 24 juin 2021 - 12:15:21
Dernière modification le : mardi 19 octobre 2021 - 11:39:12

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A. S. Prakash, P. Rozier, L. Dupont, Herve Vezin, F. Sauvage, et al.. Electrochemical Reactivity of Li2VOSiO4 toward Li. Chemistry of Materials, 2006, Chemistry of Materials, 18 (2), pp.407-412. ⟨10.1021/cm051986k⟩. ⟨hal-03269818⟩



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