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 cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca-functionalized dodecavanadate [CaVOCl(DMF)] (= ) was thus compared with that of the precursor compound (HNMe)[VOCl] (= ). can store up to five electrons per cluster, while only shows one reversible redox transition. In initial studies, we demonstrated that 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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| http://dx.doi.org/10.1039/d0sc01401j | DOI Listing |
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