Investigation of Key Electronic States in Layered Mixed Chalcogenides With a d 0 Transition Metal as Li‐Ion Cathodes

Kumar, Khagesh; Sunariwal, Neelam; Louis, Jacques; Leube, Bernhard T.; Roy, Indrani; Sterbinsky, George E.; Tarascon, Jean‐Marie; Cabana, Jordi

doi:10.1002/adfm.202408060

Title: Investigation of Key Electronic States in Layered Mixed Chalcogenides With a d ⁰ Transition Metal as Li‐Ion Cathodes

Journal Article · 06 September 2024 · Advanced Functional Materials

DOI: https://doi.org/10.1002/adfm.202408060 · OSTI ID:2440090

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^[1]; Louis, Jacques ^[2]; Leube, Bernhard T. ^[2]; Roy, Indrani ^[1];

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Department of Chemistry University of Illinois at Chicago 845W Taylor St. Chicago IL 60607 USA
Collège de France Chimie du Solide et de l’Énergie UMR 8260, 11 Place Marcelin Berthelot Paris 75231 France, Réseau Français sur le Stockage Électrochimique de l’Énergie (RS2E) 15 rue Baudelocque Amiens 80039 France
X‐Ray Science Division Advanced Photon Source Argonne National Laboratory 9700 S Cass Ave. Lemont IL 60439 USA
Department of Chemistry University of Illinois at Chicago 845W Taylor St. Chicago IL 60607 USA, Materials Science Division Argonne National Laboratory 9700 S Cass Ave. Lemont IL 60439 USA

Abstract Lithium‐rich transition metal chalcogenides are witnessing a revival as candidates for Li‐ion cathode materials, spurred by the boost in their capacities from transcending conventional redox processes based on cationic states and tapping into additional chalcogenide states. A particularly striking case is Li ₂ TiS _3‐ _y Se _y , which features a d ⁰ metal. While the end members are expectedly inactive, substantial capacities are measured when both Se and S are present. Using X‐ray absorption spectroscopy, it is shown that the electronic structure of Li ₂ TiS _3‐ _y Se _y is not a simple combination of the end members. The data confirm previous hypotheses that, in Li ₂ TiS _2.4 Se _0.6 , this behavior is underpinned by concurrent and reversible redox of only S and Se, and identify key electronic states. Moreover, wavelet transforms of the extended X‐ray absorption fine structure provide direct evidence of the formation of short Se–Se units upon charging. The study uncovers the underpinnings of this intriguing reactivity and highlights the richness of redox chemistry in complex solids.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC02-06CH11357

OSTI ID:: 2440090

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 46 Vol. 34; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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