Skip to Main content Skip to Navigation
Journal articles

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

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 Li 2 TiS 3-x Se x 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 (Se 2− /Se n−) and (S 2− /S n−) and cationic Ti 3+ /Ti 4+ 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.
Complete list of metadata

https://hal-univ-pau.archives-ouvertes.fr/hal-03354961
Contributor : Sylvie Blanc Connect in order to contact the contributor
Submitted on : Monday, September 27, 2021 - 7:58:48 AM
Last modification on : Friday, October 22, 2021 - 2:42:41 PM

File

s41467-021-25760-8.pdf
Publisher files allowed on an open archive

Licence


Distributed under a Creative Commons Attribution 4.0 International License

Identifiers

Citation

Bernhard Leube, Clara Robert, Dominique Foix, Benjamin Porcheron, R. Dedryvère, et al.. Activation of anionic redox in d0 transition metal chalcogenides by anion doping. Nature Communications, Nature Publishing Group, 2021, 12 (1), pp.5485. ⟨10.1038/s41467-021-25760-8⟩. ⟨hal-03354961⟩

Share

Metrics

Record views

63

Files downloads

46