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Redox-inactive ions control the redox-activity of molecular vanadium oxides

Greiner, S.; Schwarz, B.; Ringenberg, M.; Dürr, M.; Ivanovic-Burmazovic, I.; Fichtner, M.; Anjass, M.; Streb, C.

Abstract:
Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca$^{2+}$ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca$^{2+}$-functionalized dodecavanadate [Ca$_{2}$V$_{12}$O$_{32}$Cl(DMF) $_{3}$]$^{2-}$ (={Ca$_{2}$V$_{12}$}) was thus compared with that of the precursor compound (H$_{2}$NMe$_{2}$)$_{2}$ [V$_{12}$O$_{32}$Cl] $^{3-}$ (={V$_{12}$}). {Ca$_{2}$V$_{12}$} can store up to five electrons per cluster, while {V12} only shows one reversible redox transition. In initial studies, we demonstrated that {Ca$_{2}$V$_{12}$} can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.

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Verlagsausgabe §
DOI: 10.5445/IR/1000119886
Veröffentlicht am 13.06.2020
Originalveröffentlichung
DOI: 10.1039/d0sc01401j
Scopus
Zitationen: 3
Web of Science
Zitationen: 3
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2020
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000119886
HGF-Programm 37.01.01 (POF III, LK 01) Fundamentals and Materials
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 11
Heft 17
Seiten 4450-4455
Vorab online veröffentlicht am 06.04.2020
Nachgewiesen in Web of Science
Scopus
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