Structural and transport evolution in the LixAg2V4O11 system

F. Sauvage, V. Bodenez, H. Vezin, M. Morcrette, J. M. Tarascon, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

We investigated the effect of inserting lithium into Ag2V4O11 (ε-SVO) on the structure, electronic properties and redox committed by combining in situ XRD measurements, ESR spectroscopy and 4 probes DC conductivity coupled with thermopower measurements. The electrochemical discharge occurs in three consecutive steps above 2 V (vs. Li+/Li). The first one, between 0 <x <∼0.7 in Lix-SVO, has been ascribed to the V5+ reduction through a solid solution mechanism. This reduction competes with a Li+/Ag+ displacement reaction which leads to a structural collapse owing to the ionic radii mismatch between the withdrawn Ag+ and the inserted Li+. The silver reduction progresses continuously with two different slopes along two composition-potential plateaus at 2.81 V and 2.55 V. Finally, the reduction continues until we obtain an amorphous structure with V4+ and a ε of V3+. Although, the silver re-enters the structure during the subsequent recharge, the original structure is not recovered. The reduction of silver forming silver metal nano-clusters acts to increase the electronic conductivity from 3.8 × 10-5 S cm-1 to 1.4 × 10-3 S cm-1. In complement to this study, we also report on a low temperature hydro-(solvo)-thermal approach using HF(aq) as a mineralizer, which enables the synthesis of nano-sized ε-SVO particles that exhibit superior electrochemical performances compared to conventional particles synthesized by solid-state reaction.

Original languageEnglish
Pages (from-to)1195-1201
Number of pages7
JournalJournal of Power Sources
Volume195
Issue number4
DOIs
Publication statusPublished - Feb 15 2010

Fingerprint

Silver
silver
conductivity
in situ measurement
complement
Thermoelectric power
plateaus
Solid state reactions
solid solutions
Lithium
lithium
Electronic properties
direct current
Paramagnetic resonance
slopes
electronic structure
Solid solutions
solid state
Metals
radii

Keywords

  • AgVO
  • Cathode
  • ICD
  • In situ XRD measurements
  • Primary lithium batteries
  • SVO

ASJC Scopus subject areas

  • Electrical and Electronic Engineering
  • Energy Engineering and Power Technology
  • Renewable Energy, Sustainability and the Environment
  • Physical and Theoretical Chemistry

Cite this

Structural and transport evolution in the LixAg2V4O11 system. / Sauvage, F.; Bodenez, V.; Vezin, H.; Morcrette, M.; Tarascon, J. M.; Poeppelmeier, Kenneth R.

In: Journal of Power Sources, Vol. 195, No. 4, 15.02.2010, p. 1195-1201.

Research output: Contribution to journalArticle

Sauvage, F, Bodenez, V, Vezin, H, Morcrette, M, Tarascon, JM & Poeppelmeier, KR 2010, 'Structural and transport evolution in the LixAg2V4O11 system', Journal of Power Sources, vol. 195, no. 4, pp. 1195-1201. https://doi.org/10.1016/j.jpowsour.2009.08.091
Sauvage, F. ; Bodenez, V. ; Vezin, H. ; Morcrette, M. ; Tarascon, J. M. ; Poeppelmeier, Kenneth R. / Structural and transport evolution in the LixAg2V4O11 system. In: Journal of Power Sources. 2010 ; Vol. 195, No. 4. pp. 1195-1201.
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