PARK, Sunkyu; CHOTARD, Jean-Noël; CARLIER, Dany; MOOG, Iona; DUTTINE, Mathieu; FAUTH, François; IADECOLA, Antonella; CROGUENNEC, Laurence; MASQUELIER, Christian

doi:10.1021/acs.chemmater.2c00501

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PARK, Sunkyu
Laboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

CHOTARD, Jean-Noël
Laboratoire réactivité et chimie des solides - UMR CNRS 7314 UPJV [LRCS]
Réseau sur le stockage électrochimique de l'énergie [RS2E]

CARLIER, Dany
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
Réseau sur le stockage électrochimique de l'énergie [RS2E]

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Article de revue

Ce document a été publié dans

Chemistry of Materials. 2022, vol. 34, n° 9, p. 4142-4152

American Chemical Society

Résumé en anglais

Vanadium multi redox reactions of V4+/3+ and V5+/4+ can contribute to significant capacity gain in positive electrodes for Na-Ion batteries, but the activation of the V5+/4+ redox couple is often accompanied by asymmetric and irreversible electrochemical reactions that are very important to understand for developing high capacity materials while maintaining the structural stability. Here, the asymmetric Na+ extraction/insertion process in Fe/V-mixed NASICON Na4FeV(PO4)3 electrode material is thoroughly investigated from both local and bulk perspectives. X-ray diffraction analysis demonstrates that the Na(1) site is depopulated at the third charge domain when the V5+/4+ redox couple is activated. Local environments of Fe and V were investigated through Mössbauer and X-ray absorption spectroscopies. The results point toward the existence of a distorted VO6 octahedral environment, including a short V–O bond, when the V5+/4+ redox couple is activated at high voltage. This study presents valuable aspects of the asymmetric behavior during multielectron reactions that are commonly observed in V-based NASICON materials.< Réduire

DOI

http://dx.doi.org/10.1021/acs.chemmater.2c00501

Project ANR

Spectromètre EXAFS Rapide pour Cinétiques Chimiques - ANR-10-EQPX-0045
Laboratory of excellency for electrochemical energy storage

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Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) - UMR 5026