Phase stability and sodium-vacancy orderings in a NaSICON electrode

Ziliang Wang; Sunkyu Park; Zeyu Deng; Dany Carlier; Jean-Noël Chotard; Laurence Croguennec; Gopalakrishnan Sai Gautam; Anthony K. Cheetham; Christian Masquelier; Pieremanuele Canepa

doi:10.1039/D1TA09249A

Phase stability and sodium-vacancy orderings in a NaSICON electrode†

Ziliang Wang,^a Sunkyu Park,^bcd Zeyu Deng,

^a Dany Carlier,^cd Jean-Noël Chotard,*^bd Laurence Croguennec,

^cd Gopalakrishnan Sai Gautam,

^e Anthony K. Cheetham,

^af Christian Masquelier

^bd and Pieremanuele Canepa

*^ag

Author affiliations

* Corresponding authors

^a Department of Materials Science and Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore
E-mail: pcanepa@nus.edu.sg

^b Laboratoire de Réactivité et de Chimie des Solides (LRCS), CNRS UMR 7314, Université de Picardie Jules Verne, 80039 Amiens Cedex, France
E-mail: jean-noel.chotard@u-picardie.fr

^c CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR CNRS 5026, Pessac, France

^d RS2E, Réseau Français sur le Stockage Electrochimique de l'Energie, FR CNRS 3459, F-80039 Amiens Cedex 1, France

^e Department of Materials Engineering, Indian Institute of Science, Bengaluru, Karnataka, India

^f Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California 93106, USA

^g Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117585 Singapore, Singapore

Abstract

We elucidate the complex thermodynamics of sodium (Na) intercalation into the sodium super-ionic conductor (NaSICON)-type electrode, Na_xV₂(PO₄)₃, for promising Na-ion batteries with high-power density. This is the first report of a computational temperature-composition phase diagram of the NaSICON-type electrode Na_xV₂(PO₄)₃. Based on our computational data, we identify a thermodynamically stable phase with a composition of Na₂V₂(PO₄)₃ and describe its structural features. We also identify another metastable configuration that can occur at room temperature, namely Na_3.5V₂(PO₄)₃. We unveil the crystal-structure and the electronic-structure origins of the ground-state compositions associated with specific Na/vacancy arrangements, which are driven by charge orderings on the vanadium sites. These results are significant for the optimization of high-energy and power density electrodes for sustainable Na-ion batteries.

This article is part of the themed collection: Journal of Materials Chemistry A HOT Papers

Journal of Materials Chemistry A

Phase stability and sodium-vacancy orderings in a NaSICON electrode†

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Phase stability and sodium-vacancy orderings in a NaSICON electrode

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