The intercalation phase diagram of Mg in V$_2$O$_5$ from first principles

TL;DR

This study uses first-principles calculations to map the phase diagram of Mg intercalation in V$_2$O$_5$, revealing phase separation tendencies and highlighting the potential of the $ ext{delta}$ phase for improved Mg mobility in battery applications.

Contribution

The paper develops a comprehensive temperature-composition phase diagram for Mg in V$_2$O$_5$ using cluster expansion and first-principles calculations, providing new insights into phase behavior and mobility.

Findings

Phase separation between $ ext{alpha}$ and $ ext{delta}$ phases.

Metastable solid solution paths are possible.

Enhanced Mg mobility in the $ ext{delta}$ phase.

Abstract

We have investigated Mg intercalation into orthorhombic V$_2$O$_5$, one of only three cathodes known to reversibly intercalate Mg ions. By calculating the ground state Mg$_x$V$_2$O$_5$ configurations and by developing a cluster expansion for the configurational disorder in $\delta$-V$_2$O$_5$, a full temperature-composition phase diagram is derived. Our calculations indicate an equilibrium phase separating behavior between fully demagnesiated $\alpha$-V$_2$O$_5$ and fully magnesiated $\delta$-V$_2$O$_5$, but also motivate the existence of potentially metastable solid solution transformation paths in both phases. We find significantly better mobility for Mg in the $\delta$ polymorph suggesting that better performance can be achieved by cycling Mg in the $\delta$ phase.