The intriguing mechanism of phosphorus anodes for sodium ion batteries revealed by operando pair distribution function and X-ray diffraction computed tomography

TL;DR

This study uncovers the structural mechanisms of phosphorus anodes in sodium ion batteries using advanced operando X-ray techniques and DFT calculations, revealing distinct sodiation and desodiation pathways.

Contribution

It introduces a combined operando XRD-CT, Rietveld, PDF analysis, and DFT approach to elucidate phosphorus anode mechanisms in SIBs, which was previously unclear.

Findings

Sodiation follows a thermodynamic path from P to Na3P.

Desodiation involves a kinetically controlled deintercalation.

Layered Na3-xP structure persists until P nanoclusters form.

Abstract

Phosphorus is one of the most promising anodes for sodium ion batteries (SIBs). Little is known about the structural mechanism of Na/P cycling due to the fact that only one of the structures involved (Na3P) is crystalline. Using operando X-ray diffraction computed tomography (XRD-CT) analysed by Rietveld and pair distribution (PDF) methods combined with density functional theory (DFT) calculations we show that the sodiation and desodiation mechanisms of phosphorus are very different. Sodiation follows the thermodynamic path of lowest energy from P via NaP to Na3P while desodiation follows a kinetically controlled deintercalation mechanism in which the layered Na3-xP type structure is maintained until P nanoclusters form. Using XRD-CT allows analysis of the 3D structure of the anode, but most importantly, removes the contributions from the sample container and other battery components, particularly important for PDF analysis.