Issue 41, 2024

Reversible multielectron redox activity of the anti-NASICON-type phosphate LiNbV(PO4)3 towards lithium and sodium intercalation

Abstract

The LiNbV(PO4)3 phosphate with the anti-NASICON structure (a = 12.126(1) Å, b = 8.6158(4) Å, c = 8.6959(6) Å, V = 908.5(1) Å3, S.G. Pbcn) has been synthesized using a Pechini sol–gel process. It exhibits reversible multielectron transitions versus Li and Na anodes. In a Li half-cell, it supports a 4e transfer due to the activation of the Nb5+/Nb3+ and V4+/V2+ redox couples, being the first example of 4d metal redox transitions within the anti-NASICON framework confirmed by XANES measurements. X-ray diffraction performed in ex situ and operando regimes disclosed a single-phase mechanism of lithium (de)intercalation. In a Na half-cell, the material demonstrates reversible uptake of 2.77 Na+ ions. Density functional theory calculations revealed percolation barriers of ∼0.5–0.7 eV for Na+ hopping, thus supporting the activation of Na+ ion diffusion in the NbV(PO4)3 framework. This study introduces a new approach to improve anti-NASICON-structured electrode materials by utilizing redox transitions of 4d elements for energy storage.

Graphical abstract: Reversible multielectron redox activity of the anti-NASICON-type phosphate LiNbV(PO4)3 towards lithium and sodium intercalation

Supplementary files

Article information

Article type
Paper
Submitted
15 Jul 2024
Accepted
19 Sep 2024
First published
01 Oct 2024

Dalton Trans., 2024,53, 16918-16928

Reversible multielectron redox activity of the anti-NASICON-type phosphate LiNbV(PO4)3 towards lithium and sodium intercalation

I. R. Cherkashchenko, R. V. Panin, A. D. Dembitskiy, D. A. Novichkov, D. A. Aksyonov, E. V. Antipov and N. R. Khasanova, Dalton Trans., 2024, 53, 16918 DOI: 10.1039/D4DT02031F

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