Electrochemical Exploration of Layered Cu-Based Oxychalcogenides Obtained Topochemically via Anionic Redox and Displacement Reaction - Université de Pau et des Pays de l'Adour Accéder directement au contenu
Article Dans Une Revue Chemistry of Materials Année : 2023

Electrochemical Exploration of Layered Cu-Based Oxychalcogenides Obtained Topochemically via Anionic Redox and Displacement Reaction

Anshuman Chaupatnaik
Gwenaëlle Rousse
Jacques Louis
  • Fonction : Auteur
Bernhard Leube

Résumé

Li-rich oxides, operating partially on high-voltage anionic redox, permit energy densities larger than electrode materials relying solely on transition-metal redox. On the contrary, Li-rich sulfides present a lower hysteresis but operate at a lower voltage. Oxysulfide electrodes, if adequately designed, can bridge this gap and offer high energy density with a minor penalty of hysteresis or capacity. Tetragonal-layered CuMOX (M = Bi/La, X = S/Se) chalcogenides are explored in this direction, and we found that Cu can be extracted at room temperature both electrochemically and chemically with different outcomes, some of which lead to new layered monoclinic bismuth “oxyperchalcogenide” oxidized phases, BiOX*, with dimerized S/Se. Moreover, we show that these new BiOX* phases can insert lithium to form new tetragonal-layered LiBiOX phases, isostructural to pristine CuBiOX. Both the CuBiOX and BiOX* phases are shown to insert four lithium ions via conversion and intercalation–conversion reactions, respectively. Further, we demonstrate the importance of the host cation on the above insertion reactivity by replacing Bi with La to produce a new layered tetragonal phase Cu1–xLixLaOS. The encountered different reaction pathways are rationalized by theoretical calculations. This work shows that Cu-based layered oxychalcogenides can offer rich hunting grounds for new metastable electrochemically active layered materials.
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Dates et versions

hal-04170694 , version 1 (25-07-2023)

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Anshuman Chaupatnaik, Artem Abakumov, Gwenaëlle Rousse, Dominique Foix, Jacques Louis, et al.. Electrochemical Exploration of Layered Cu-Based Oxychalcogenides Obtained Topochemically via Anionic Redox and Displacement Reaction. Chemistry of Materials, 2023, 35 (15), pp.5924-5935. ⟨10.1021/acs.chemmater.3c00803⟩. ⟨hal-04170694⟩
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