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On the strange case of divalent ions intercalation in V2O5

Verrelli, Roberta and Black, Ashley Philip and Pattanathummasid, Chanachai and Tchitchekova, Deyana S. and Ponrouch, Alexandre and Oró-Solé, Judith and Frontera, Carlos and Bardé, Fanny and Rozier, Patrick and Palacín, Rosa On the strange case of divalent ions intercalation in V2O5. (2018) Journal of Power Sources, 407. 162-172. ISSN 0378-7753

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Official URL: https://doi.org/10.1016/j.jpowsour.2018.08.024

Abstract

Vanadium pentoxide has been investigated for multivalent ion battery technologies but the structural characterization of inserted phases is poor, and conflicting reports exist in the literature. This study presents a critical overview of controversial aspects related to Mg and Ca insertion in α-V2O5 under diverse conditions by combined electrochemical and ex-situ XRD experiments. Galvanostatic tests are carried out in dry and wet alkyl carbonate-based electrolytes at RT and 100 °C. The formation of protonated phases with negligible divalent ion content if any is evidenced by Rietveld refinements of the XRD data, unambiguously dismissing the presence of AV2O5 (A: Mg, Ca) as electrochemical reduction products. Furthermore, thermal instability of V2O5 at 100 °C in alkyl carbonate solvents is demonstrated by XRD and TEM analysis and the formation of an orthorhombic phase with increased a parameter, most likely due to degradation favored by both water and temperature, is observed for both Mg and Ca. In order to assess the feasibility of the reverse reaction, fully intercalated AV2O5 (A = Ca, Mg) phases were also prepared by solid state reaction and oxidation attempted both electrochemically and chemically without evidence of any significant amount of Mg2+ or Ca2+ extraction, further corroborating the sluggish diffusion kinetics of divalent cations in α-V2O5.

Item Type:Article
HAL Id:hal-02350555
Audience (journal):International peer-reviewed journal
Uncontrolled Keywords:
Institution:French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE)
Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Other partners > Toyota Motor Europe (BELGIUM)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Universitat Autònoma de Barcelona - UAB (SPAIN)
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Deposited On:06 Nov 2019 08:11

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