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

Greiner, S. 1; Schwarz, B.; Ringenberg, M.; Dürr, M.; Ivanovic-Burmazovic, I.; Fichtner, M. 2; Anjass, M. 1; Streb, C. 1
1 Karlsruher Institut für Technologie (KIT)
2 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)


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.

Verlagsausgabe §
DOI: 10.5445/IR/1000119886
Veröffentlicht am 13.06.2020
DOI: 10.1039/d0sc01401j
Zitationen: 19
Web of Science
Zitationen: 18
Zitationen: 23
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 Dimensions
Web of Science
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