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Title: Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes

Abstract

Structural studies have been carried out on Ag{sub 2}V{sub 4}O{sub 11} (silver vanadium oxide, SVO) and Li{sub x}Ag{sub 2}V{sub 4}O{sub 11}, lithiated SVO with x=0.72, 2.13, and 5.59 using nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Lithium-7 NMR indicates the formation of a solid electrolyte interphase layer on the x=0.72 sample and lithium intercalation into both octahedral and tetrahedral sites in the SVO lattice, and that most but not all of the Ag (I) is reduced prior to initiation of V(V) reduction. Vanadium-51 NMR studies of SVO and lithiated SVO show decreased crystallinity with increased lithiation, as previously reported. Silver XAS studies indicate the formation of metallic silver crystallites in all the lithiated samples. A comparison of X-ray absorption near edge spectroscopy spectra for vanadium in these samples with those of reference compounds shows that some reduction of vanadium (V) occurs in the lithiated SVO with x=0.72 and increases with further lithiation leading to the formation of V(IV) and V(III) species. The results of this study indicate that vanadium(V) reduction occurs in parallel with silver (I) reduction during the initial stages of SVO lithiation, leading ultimately to the formation of vanadium (IV) and (III) species with further lithiation.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930344
Report Number(s):
BNL-81057-2008-JA
Journal ID: ISSN 0013-4651; JESOAN; TRN: US200904%%637
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the Electrochemical Society; Journal Volume: 154; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION SPECTROSCOPY; CATHODES; CRYSTAL STRUCTURE; CRYSTALS; LITHIUM; LITHIUM 7; NUCLEAR MAGNETIC RESONANCE; SILVER; SOLID ELECTROLYTES; SPECTRA; SPECTROSCOPY; VANADIUM; VANADIUM 51; VANADIUM OXIDES; X-RAY SPECTROSCOPY; national synchrotron light source

Citation Formats

Leifer,N., Colon, A., Martocci, k., Greenbaum, S., Alamgir, F., Reddy, T., Gleason, N., Leising, R., and Takeuchi, E. Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes. United States: N. p., 2007. Web. doi:10.1149/1.2718402.
Leifer,N., Colon, A., Martocci, k., Greenbaum, S., Alamgir, F., Reddy, T., Gleason, N., Leising, R., & Takeuchi, E. Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes. United States. doi:10.1149/1.2718402.
Leifer,N., Colon, A., Martocci, k., Greenbaum, S., Alamgir, F., Reddy, T., Gleason, N., Leising, R., and Takeuchi, E. Mon . "Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes". United States. doi:10.1149/1.2718402.
@article{osti_930344,
title = {Nuclear Magnetic Resonance and X-Ray Absorption Spectroscopic Studies of Lithium Insertion in Silver Vanadium Oxide Cathodes},
author = {Leifer,N. and Colon, A. and Martocci, k. and Greenbaum, S. and Alamgir, F. and Reddy, T. and Gleason, N. and Leising, R. and Takeuchi, E.},
abstractNote = {Structural studies have been carried out on Ag{sub 2}V{sub 4}O{sub 11} (silver vanadium oxide, SVO) and Li{sub x}Ag{sub 2}V{sub 4}O{sub 11}, lithiated SVO with x=0.72, 2.13, and 5.59 using nuclear magnetic resonance (NMR) and X-ray absorption spectroscopy (XAS). Lithium-7 NMR indicates the formation of a solid electrolyte interphase layer on the x=0.72 sample and lithium intercalation into both octahedral and tetrahedral sites in the SVO lattice, and that most but not all of the Ag (I) is reduced prior to initiation of V(V) reduction. Vanadium-51 NMR studies of SVO and lithiated SVO show decreased crystallinity with increased lithiation, as previously reported. Silver XAS studies indicate the formation of metallic silver crystallites in all the lithiated samples. A comparison of X-ray absorption near edge spectroscopy spectra for vanadium in these samples with those of reference compounds shows that some reduction of vanadium (V) occurs in the lithiated SVO with x=0.72 and increases with further lithiation leading to the formation of V(IV) and V(III) species. The results of this study indicate that vanadium(V) reduction occurs in parallel with silver (I) reduction during the initial stages of SVO lithiation, leading ultimately to the formation of vanadium (IV) and (III) species with further lithiation.},
doi = {10.1149/1.2718402},
journal = {Journal of the Electrochemical Society},
number = 6,
volume = 154,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}