Elucidating the LiFePO4 air aging mechanism to predict its electrochemical performance

Marine Cuisinier; Jean-Frédéric Martin; Nicolas Dupré; Ryoji Kanno; Dominique Guyomard

doi:10.1039/C1JM12649K

Elucidating the LiFePO₄ air aging mechanism to predict its electrochemical performance†

Marine Cuisinier,^a Jean-Frédéric Martin,^ab Nicolas Dupré,*^a Ryoji Kanno^b and Dominique Guyomard^a

* Corresponding authors

^a Institut des Matériaux Jean Rouxel (IMN) Université de Nantes—CNRS, UMR6502, 2 rue de la Houssinière B.P.32229, Nantes Cedex 3, France
E-mail: nicolas.dupre@cnrs-imn.fr
Fax: +33 2 40 37 39 95
Tel: +33 2 40 37 39 33

^b Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama, Japan

Abstract

Although LiFePO₄-based chemistry has been extensively studied and developed in the last decade due to its promise for the next generation of Li-ion battery applications, the impact of ambient air exposure and the concomitant aging mechanism is still a controversial matter. In the present study, we describe quantitatively the aging process in terms of the successive phase formation, distribution and iron local environments. Formation and growth of a disordered ferric phosphate phase are directly observed for the first time from the surface of particles toward the core, preceding the crystallization of tavorite LiFePO₄(OH) as observed through the combination of amorphous phase quantification by XRD, and by Mössbauer and Electron Energy Loss spectroscopies. Structural and electrochemical characterization prove that the amorphous ferric phosphate formed in the early aging stage exhibits already tavorite composition and structure at the local scale and shed light on a crucial step of the aging mechanism. Based on the correlation we establish here between the amounts of Fe(III) and hydroxyls groups present in aged samples and specific capacity of the corresponding electrodes, we show that the degradation of active material upon storage and the electrochemical performance can be predicted easily through simple TGA measurements.

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DOI: https://doi.org/10.1039/C1JM12649K
Article type: Paper
Submitted: 09 Jun 2011
Accepted: 09 Sep 2011
First published: 24 Oct 2011

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J. Mater. Chem., 2011,21, 18575-18583

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Elucidating the LiFePO₄ air aging mechanism to predict its electrochemical performance

M. Cuisinier, J. Martin, N. Dupré, R. Kanno and D. Guyomard, J. Mater. Chem., 2011, 21, 18575 DOI: 10.1039/C1JM12649K

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Journal of Materials Chemistry

Elucidating the LiFePO₄ air aging mechanism to predict its electrochemical performance†

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Elucidating the LiFePO₄ air aging mechanism to predict its electrochemical performance

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