Issue 1, 2021

A chemical map of NaSICON electrode materials for sodium-ion batteries

Abstract

Na-ion batteries are promising devices for smart grids and electric vehicles due to the cost effectiveness arising from the overall abundance of sodium (Na) and its even geographical distribution. Among other factors, the energy density of Na-ion batteries is limited by the cathode electrode chemistry. NaSICON-based electrode materials are known for their wide range of electrochemical potentials, high ionic conductivity, and most importantly their structural and thermal stabilities. Using first-principles calculations, we chart the chemical space of 3d transition metal-based NaSICON phosphates with the formula NaxMM′(PO4)3 (with M and M′ = Ti, V, Cr, Mn, Fe, Co and Ni) to analyze their thermodynamic stabilities and the intercalation voltages for Na+ ions. Specifically, we compute the Na insertion voltages and related properties of 28 distinct NaSICON compositions. We investigate the thermodynamic stability of Na-intercalation in previously unreported NaxMn2(PO4)3 and NaxVCo(PO4)3. The calculated quaternary phase diagrams of the Na–P–O–Co and Na–P–O–Ni chemical systems explain the origin of the suspected instability of Ni and Co-based NaSICON compositions. From our analysis, we are also able to rationalize anomalies in previously reported experimental data in this diverse and important chemical space.

Graphical abstract: A chemical map of NaSICON electrode materials for sodium-ion batteries

Supplementary files

Article information

Article type
Paper
Submitted
02 11 2020
Accepted
21 11 2020
First published
23 11 2020

J. Mater. Chem. A, 2021,9, 281-292

A chemical map of NaSICON electrode materials for sodium-ion batteries

B. Singh, Z. Wang, S. Park, G. S. Gautam, J. Chotard, L. Croguennec, D. Carlier, A. K. Cheetham, C. Masquelier and P. Canepa, J. Mater. Chem. A, 2021, 9, 281 DOI: 10.1039/D0TA10688G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements