Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration

Rao, K. J. ; Pecquenard, B. ; Gies, A. ; Levasseur, A. ; Etourneau, J. (2006) Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration Bulletin of Materials Science, 29 (5). pp. 535-546. ISSN 0250-4707

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Official URL: http://www.ias.ac.in/matersci/bmsoct2006/535.pdf

Abstract

Structural and electrochemical aspects of vanadium oxide films recently reported from ICMCB/ENSCPB have been examined using appropriate structural models. It is shown that amorphous films are nonstoichiometric as a result of pre-deposition decomposition of V2O5. It is proposed that the structure of amorphous films corresponds to a nanotextured mosaic of V2O5 and V2O4 regions. Lithium intercalation into these regions is considered to occur sequentially and determined by differences in group electronegativities. Open circuit voltages (OCV) have been calculated for various stoichiometric levels of lithiation using available thermodynamic data with approximate corrections. Sequestration of lithium observed in experiments is shown to be an interfacial phenomenon. X-ray photoelectron spectroscopic observation of the formation of V3+ even when V5+ has not been completely reduced to V4+ is shown to be entirely consistent with the proposed structural model and a consequence of initial oxygen nonstoichiometry. Based on the structural data available on V2O5 and its lithiated products, it is argued that the geometry of VOn polyhedron changes from square pyramid to trigonal bipyramid to octahedron with increase of lithiation. A molecular orbital based energy band diagram is presented which suggests that lithiated vanadium oxides, LixV2O5, become metallic for high values of x.

Item Type:Article
Source:Copyright of this article belongs to Indian Academy of Sciences.
Keywords:Amorphous Films; Vanadium Oxide Films; Structural and Electrochemical Properties
ID Code:91031
Deposited On:16 May 2012 08:35
Last Modified:19 May 2016 05:00

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