Investigating the Role of Structural Water on the Electrochemical Properties of $\alpha$-V$_2$O$_5$ through Density Functional Theory

TL;DR

This study uses density functional theory to explore how structural water in $ ext{V}_2 ext{O}_5$ affects its electrochemical properties, including voltage and ion diffusion, for various intercalating ions.

Contribution

It provides a systematic analysis of how structural water alters voltage, diffusion barriers, and electrostatic environment in $ ext{V}_2 ext{O}_5$, revealing mechanisms behind improved electrochemical performance.

Findings

Water coordination increases voltage and energy density.

Interlayer distance and charge shielding affect diffusion kinetics.

Diffusion barriers for Mg and Ca decrease significantly with water presence.

Abstract

The $\alpha$ polymorph of V$_2$O$_5$ is one of the few known cathodes capable of reversibly intercalating multivalent ions such as Mg, Ca, Zn and Al, but suffers from sluggish diffusion kinetics. The role of H$_2$O within the electrolyte and between the layers of the structure in the form of a xerogel/aerogel structure, though, has been shown to lower diffusion barriers and lead to other improved electrochemical properties. This density functional theory study systematically investigates how and why the presence of structural H$_2$O within $\alpha$-V$_2$O$_5$ changes the resulting structure, voltage, and diffusion kinetics for the intercalation of Li, Na, Mg, Ca, Zn, and Al. We found that the coordination of H$_2$O molecules with the ion leads to an improvement in voltage and energy density for all ions. This voltage increase was attributed to the extra host sites for electrons present with H$_2$O, thus leading to a stronger ionization of the ion and a higher voltage. We also found that the increase in interlayer distance and a potential "charge shielding" effect drastically changes the electrostatic environment and the resulting diffusion kinetics. For Mg and Ca, this resulted in a decrease in diffusion barrier from 1.3 eV and 2.0 eV to 0.89 eV and 0.4 eV, respectively. We hope that our study motivates similar research regarding the role of water in both V$_2$O$_5$ xerogels/aerogels and other layered transition metal oxides.