Activation of anionic redox in d0 transition metal chalcogenides by anion doping

Bernhard T. Leube, Clara Robert, Dominique Foix, Benjamin Porcheron, Remi Dedryvère, Gwenaëlle Rousse, Elodie Salager, Pierre-Etienne Cabelguen, Artem M. Abakumov, Hervé Vezin, Marie-Liesse Doublet and Jean-Marie Tarascon ()
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Bernhard T. Leube: UMR 8260
Clara Robert: FR CNRS 3459
Dominique Foix: FR CNRS 3459
Benjamin Porcheron: FR CNRS 3459
Remi Dedryvère: FR CNRS 3459
Gwenaëlle Rousse: UMR 8260
Elodie Salager: FR CNRS 3459
Pierre-Etienne Cabelguen: New Business Incubation
Artem M. Abakumov: Skolkovo Institute of Science and Technology
Hervé Vezin: UMR CNRS 8516 LASIRE,
Marie-Liesse Doublet: FR CNRS 3459
Jean-Marie Tarascon: UMR 8260

Nature Communications, 2021, vol. 12, issue 1, 1-11

Abstract: Abstract Expanding the chemical space for designing novel anionic redox materials from oxides to sulfides has enabled to better apprehend fundamental aspects dealing with cationic-anionic relative band positioning. Pursuing with chalcogenides, but deviating from cationic substitution, we here present another twist to our band positioning strategy that relies on mixed ligands with the synthesis of the Li2TiS3-xSex solid solution series. Through the series the electrochemical activity displays a bell shape variation that peaks at 260 mAh/g for the composition x = 0.6 with barely no capacity for the x = 0 and x = 3 end members. We show that this capacity results from cumulated anionic (Se2−/Sen−) and (S2−/Sn−) and cationic Ti3+/Ti4+ redox processes and provide evidence for a metal-ligand charge transfer by temperature-driven electron localization. Moreover, DFT calculations reveal that an anionic redox process cannot take place without the dynamic involvement of the transition metal electronic states. These insights can guide the rational synthesis of other Li-rich chalcogenides that are of interest for the development of solid-state batteries.

Date: 2021
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DOI: 10.1038/s41467-021-25760-8

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