Vanadium-Substituted Tunnel Structured Silver Hollandite (Ag1.2 Vx Mn8-x O16 ): Impact on Morphology and Electrochemistry

Inorganic Chemistry
Paul F SmithKenneth J Takeuchi

Abstract

A series of tunnel structured V-substituted silver hollandite (Ag1.2V x Mn8-xO16, x = 0-1.4) samples is prepared and characterized through a combination of synchrotron X-ray diffraction (XRD), synchrotron X-ray absorption spectroscopy (XAS), laboratory Raman spectroscopy, and electron microscopy measurements. The oxidation states of the individual transition metals are characterized using V and Mn K-edge XAS data indicating the vanadium centers exist as V5+, and the Mn oxidation state decreases with increased V substitution to balance the charge. Scanning transmission electron microscopy of reduced materials shows reduction-displacement of silver metal at high levels of lithiation. In lithium batteries, the V-substituted tunneled manganese oxide materials reveal previously unseen reversible nonaqueous Ag electrochemistry and exhibit up to 2.5× higher Li storage capacity relative to their unsubstituted counterparts. The highest capacity was observed for the Ag1.2(V0.8Mn7.2)O16·0.8H2O material with an intermediate level of V substitution, likely due to a combination of the atomic composition, the morphology of the particle, and the homogeneous distribution of the active material within the electrode structure where factors over m...Continue Reading

References

Aug 6, 2000·Acta Crystallographica. Section B, Structural Science·P Y Zavalij, M S Whittingham
Sep 21, 2002·Chemical Communications : Chem Comm·S ChingS L Suib
Jan 30, 2004·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·C M JulienC Poinsignon
Jun 24, 2004·Journal of the American Chemical Society·Mihai PolverejanSteven L Suib
Mar 16, 2012·Angewandte Chemie·Zhiwei HuangXingfu Tang
Oct 11, 2012·ACS Applied Materials & Interfaces·Kenneth J TakeuchiEsther S Takeuchi
Apr 8, 2014·Physical Chemistry Chemical Physics : PCCP·Kevin C KirshenbaumEsther S Takeuchi
Feb 20, 2018·Accounts of Chemical Research·Lisa M HouselEsther S Takeuchi

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