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Review

Towards Reversible High-Voltage Multi-Electron Reactions in Alkali-Ion Batteries Using Vanadium Phosphate Positive Electrode Materials

1
Laboratoire de Réactivité et de Chimie des Solides, CNRS-UMR 7314, Université de Picardie Jules Verne, CEDEX 1, F-80039 Amiens, France
2
CNRS, Université Bordeaux, Bordeaux INP, ICMCB UMR 5026, F-33600 Pessac, France
3
RS2E, Réseau Français sur le Stockage Electrochimique de l’Energie, FR CNRS 3459, CEDEX 1, F-80039 Amiens, France
4
ALISTORE-ERI European Research Institute, FR CNRS 3104, CEDEX 1, F-80039 Amiens, France
*
Author to whom correspondence should be addressed.
Academic Editor: Myung-Hwan Whangbo
Molecules 2021, 26(5), 1428; https://doi.org/10.3390/molecules26051428
Received: 30 January 2021 / Revised: 24 February 2021 / Accepted: 1 March 2021 / Published: 6 March 2021
Vanadium phosphate positive electrode materials attract great interest in the field of Alkali-ion (Li, Na and K-ion) batteries due to their ability to store several electrons per transition metal. These multi-electron reactions (from V2+ to V5+) combined with the high voltage of corresponding redox couples (e.g., 4.0 V vs. for V3+/V4+ in Na3V2(PO4)2F3) could allow the achievement the 1 kWh/kg milestone at the positive electrode level in Alkali-ion batteries. However, a massive divergence in the voltage reported for the V3+/V4+ and V4+/V5+ redox couples as a function of crystal structure is noticed. Moreover, vanadium phosphates that operate at high V3+/V4+ voltages are usually unable to reversibly exchange several electrons in a narrow enough voltage range. Here, through the review of redox mechanisms and structural evolutions upon electrochemical operation of selected widely studied materials, we identify the crystallographic origin of this trend: the distribution of PO4 groups around vanadium octahedra, that allows or prevents the formation of the vanadyl distortion (OV4+=O or OV5+=O). While the vanadyl entity massively lowers the voltage of the V3+/V4+ and V4+/V5+ couples, it considerably improves the reversibility of these redox reactions. Therefore, anionic substitutions, mainly O2− by F, have been identified as a strategy allowing for combining the beneficial effect of the vanadyl distortion on the reversibility with the high voltage of vanadium redox couples in fluorine rich environments. View Full-Text
Keywords: batteries; positive electrode; vanadium phosphates; covalent vanadyl bond; mixed anion batteries; positive electrode; vanadium phosphates; covalent vanadyl bond; mixed anion
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MDPI and ACS Style

Boivin, E.; Chotard, J.-N.; Masquelier, C.; Croguennec, L. Towards Reversible High-Voltage Multi-Electron Reactions in Alkali-Ion Batteries Using Vanadium Phosphate Positive Electrode Materials. Molecules 2021, 26, 1428. https://doi.org/10.3390/molecules26051428

AMA Style

Boivin E, Chotard J-N, Masquelier C, Croguennec L. Towards Reversible High-Voltage Multi-Electron Reactions in Alkali-Ion Batteries Using Vanadium Phosphate Positive Electrode Materials. Molecules. 2021; 26(5):1428. https://doi.org/10.3390/molecules26051428

Chicago/Turabian Style

Boivin, Edouard, Jean-Noël Chotard, Christian Masquelier, and Laurence Croguennec. 2021. "Towards Reversible High-Voltage Multi-Electron Reactions in Alkali-Ion Batteries Using Vanadium Phosphate Positive Electrode Materials" Molecules 26, no. 5: 1428. https://doi.org/10.3390/molecules26051428

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