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Issue 28, 2016
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Structural and electrochemical studies of a new Tavorite composition: LiVPO4OH

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Abstract

Polyanionic materials attract strong interest in the field of Li-ion battery research thanks to the wide range of compositions, structures and electrochemical properties they offer. Tavorite-type compositions offer a very rich crystal chemistry, among which LiVPO4F has the highest theoretical energy density (i.e. 655 W h kg−1). A new Tavorite-type LiVPO4OH composition was synthesized by a hydrothermal route from three different vanadium-containing precursors. The crystal structure of this new phase was fully determined thanks to synchrotron X-ray and neutron diffraction. 1H, 7Li, and 31P magic angle spinning nuclear magnetic resonance spectroscopy as well as diffuse reflectance infra-red spectroscopy were performed in order to support further the nature of the phases formed. Galvanostatic intermittent titration technique experiments in lithium batteries and ex situ X-ray diffraction analyses revealed that during oxidation the concomitant extraction of Li+ and H+ occurs at the same equilibrium potential (3.95 V vs. Li+/Li) and leads to the formation of the Tavorite phase VPO4O at the end of the charge. LiVPO4OH is also electrochemically active in the low voltage region, upon Li+ insertion. The reversible insertion/extraction of lithium at 1.35 V vs. Li+/Li leads to the formation of Li2VPO4OH at the end of discharge.

Graphical abstract: Structural and electrochemical studies of a new Tavorite composition: LiVPO4OH

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Supplementary files

Article information


Submitted
21 Apr 2016
Accepted
16 Jun 2016
First published
16 Jun 2016

J. Mater. Chem. A, 2016,4, 11030-11045
Article type
Paper

Structural and electrochemical studies of a new Tavorite composition: LiVPO4OH

E. Boivin, J. Chotard, M. Ménétrier, L. Bourgeois, T. Bamine, D. Carlier, F. Fauth, E. Suard, C. Masquelier and L. Croguennec, J. Mater. Chem. A, 2016, 4, 11030
DOI: 10.1039/C6TA03339C

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