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 ofx.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Bullet D W 1980J. Phys. C13 L595
Carathers E, Kleinmann L and Zang H I 1973Phys. Rev. B7 3753
Chandrappa G T, Steunou N and Livage J 2002Nature 416 702
Clark R J H 1968The chemistry of the vanadium and the titanium (New York)
Cocciantelli J M, Menetrier M, Delmas C, Doumerc J P, Pouchard M and Hagenmuller P 1992Solid State Ionics 50 99
Delmas C, Brethes S and Menetrier M 1991J. Power Sources 34 113
Delmas C, Cognac-Auradou H, Cocciantelli J M, Menetrier M and Doumerc J P 1994Solid State Ionics 69 257
Enjalbert R and Galy J 1986Acta Crystallogr. C, Cryst. Struct. Commun. 11 1467
Eyert V and Hock K H 1998Phys. Rev. B57 12727
Galy J, Darriet J and Hagenmuller P 1971Rev. Chim. Min. 8 509
Gies A, Pecquenard B, Benayad A, Martinez H, Gonbeau D, Fuess H and Levasseur A 2005Solid State Ionics 176 1627
Herbert C, Willinger M, Su D S, Pongratz P, Schattchneider P and Schologl R 2002Eur. Phys. J. B28 407
Hermann K, Chakrabarti A, Haras A, Witko M and Tepper B 2001Phys. Status Solidi (a) 187 137
JANAF Thermodynamic Tables 1998 ACS, APS and NIST: New York, 11th Edition
Kurmaer E Zet al 1998J. Phys. Cond. Matter 10 4081
Mattheiss L F 1994J. Phys. Cond. Matter 6 6477
Muhr H J, Krumeich F, Schönholzer U P, Bieri F, Niederberger M, Ganckler L J and Nesper R 2000Adv. Mater. 12 231
Müller U 1993Inorganic structural chemistry (New York)
Pereira-Ramos J P, Messina R, Znaidi L and Baffier N 1988Solid State Ionics 1 886
Rocquefelte X, Boucher F, Gressier P and Ouvrard G 2003Chem. Mater. 15 1812
Sanderson R T 1976Chemical bonds and bond energy (New York: Academic Press)
Sanderson R T 1983Polar covalence (New York: Academic Press)
Schwingenschlogl U, Eyert V and Eckern U 2003Europhys. Lett. 64 682
Ven A V D, Aydinol M K, Ceder G, Kresse G and Hofner J 1998Phys. Rev. B58 2975
Wang Y W, Xu H Y, Wang H, Zhang Y C, Song Z Q, Yan H and Wan C R 2004Solid State Ionics 167 419
Wells A F 1995Structural inorganic chemistry (New York)
West K, Zachau-Christiansen B, Jacobsen T and Skaarup S 1995Solid State Ionics 76 15
Zavalij P Y and Whittingham M S 1999Acta Crystallogr. B55 627
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Rao, K.J., Pecquenard, B., Gies, A. et al. Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration. Bull Mater Sci 29, 535–546 (2006). https://doi.org/10.1007/BF02914086
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02914086