Exploration of amorphous V$_2$O$_5$ as cathode for magnesium batteries

TL;DR

This study explores amorphous V$_2$O$_5$ as a cathode material for magnesium batteries, demonstrating high Mg$^{2+}$ diffusivity and promising energy density, using advanced computational modeling techniques.

Contribution

The paper introduces a novel application of amorphous V$_2$O$_5$ as a magnesium battery cathode, supported by ab initio and machine learning simulations showing enhanced ion mobility.

Findings

Amorphous V$_2$O$_5$ maintains higher voltage than sulfide cathodes.

Mg$^{2+}$ diffusivity in amorphous V$_2$O$_5$ is 5-7 orders of magnitude higher than in crystalline form.

Mg$^{2+}$ motion is cross-correlated at low temperatures, decreasing with temperature.

Abstract

Development of energy storage technologies that can exhibit higher energy densities, better safety, and lower supply-chain constraints than the current state-of-the-art Li-ion batteries (LIBs) is crucial for our transition into sustainable energy use. In this context, Mg batteries (MBs) offer a promising pathway to design energy storage systems with superior volumetric energy densities than LIBs but require the development of positive electrodes (cathodes) exhibiting high energy and power densities. Notably, amorphous materials that lack long range order can exhibit `flatter' potential energy surfaces than crystalline frameworks, possibly resulting in faster Mg$^{2+}$ motion. Here, we use a combination of ab initio molecular dynamics (AIMD), and machine learned interatomic potential (MLIP) based calculations to explore amorphous V$_2$O$_5$ as a potential cathode for MBs. Using an AIMD-generated dataset, we train and validate moment tensor potentials that can accurately model amorphous (Mg)V$_2$O$_5$ Due to the amorphization of V$_2$O$_5$, we observe a 10-14% drop in the average Mg intercalation voltage $-$ but the voltage remains higher than sulfide Mg cathodes. Importantly, we find a $\sim$seven (five) orders of magnitude higher Mg$^{2+}$ diffusivity in amorphous MgV$_2$O$_5$ than its crystalline version (thiospinel-Mg$_x$Ti$_2$S$_4$), which is directly attributable to the amorphization of the structure. Also, we note the Mg$^{2+}$ motion in the amorphous structure is significantly cross-correlated at low temperatures, with the correlation decreasing with increase in temperature. Thus, our work highlights the potential of amorphous V$_2$O$_5$ as a cathode that can exhibit both high energy and power densities, resulting in the practical deployment of MBs.