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Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
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Academic Editor: Amor M. Abdelkader
Molecules 2019, 24(10), 1893; https://doi.org/10.3390/molecules24101893
Received: 17 April 2019 / Revised: 7 May 2019 / Accepted: 13 May 2019 / Published: 16 May 2019
(This article belongs to the Special Issue Advances in Electrochemical Energy Storage Devices)
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Abstract

Solid-solution Li-ion cathode materials transform through a single-phase reaction thus leading to a long-term structural stability and improved cyclability. In this work, a two- to single-phase Li+-extraction/insertion mechanism is studied through tuning the stoichiometry of transition-metal Fe/V cations to trigger a transition in the chemical reactivity path. Tavorite triclinic-structured LiFe1−xVxPO4F (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) solid-solution powders were prepared by a facile one-step solid-state method from hydrothermal-synthesized and commercial raw materials. The broad shape of cyclic voltammetry (CV) peaks, sloping charge/discharge profiles and sloping open-circuit voltage (OCV) profiles were observed in LiFe1−xVxPO4F solid-solution cathodes while 0 < x < 1. These confirm strongly a single-phase behavior which is different from the two-phase behavior in the end-members (x = 0 or 1). The electronegativity of M (M = Fe1−xVx) for the redox potential of Fe2+/3+ couple or the M–O4F2 bond length for the V3+/4+ couple plays respectively a dominant role in LiFe1−xVxPO4F solid-solution cathodes. View Full-Text
Keywords: LiFePO4F–LiVPO4F; solid solution; single-phase reaction; redox potential; diffusion coefficient LiFePO4F–LiVPO4F; solid solution; single-phase reaction; redox potential; diffusion coefficient
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Yan, J.-L.; Shao, G.-Q.; Fan, S.-H.; Zhu, C.; Zhang, Y.; Wang, J.; Liu, Q. Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes. Molecules 2019, 24, 1893.

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