Impact of Intermediate Sites on Bulk Diffusion Barriers: Mg Intercalation in Mg$_2$Mo$_3$O$_8$

TL;DR

This study investigates Mg intercalation in Mg$_2$Mo$_3$O$_8$, revealing high diffusion barriers and structural instability that hinder its use as a Mg battery electrode, despite some chemical demagnesiation success.

Contribution

The paper combines experimental and first-principles calculations to analyze Mg diffusion pathways and barriers in Mg$_2$Mo$_3$O$_8$, highlighting the impact of transition states on Mg mobility.

Findings

No electrochemical activity observed for Mg intercalation.

Chemical demagnesiation leads to amorphization of the material.

High Mg diffusion barriers due to transition state structures.

Abstract

The ongoing search for high voltage positive electrode materials for Mg batteries has been primarily hampered by poor Mg mobility in bulk oxide frameworks. Motivated by the presence of Mo$_3$ clusters that can facilitate charge redistribution and the presence of Mg in a non-preferred (tetrahedral) coordination environment, we have investigated the Mg (de)intercalation behavior in layered-Mg$_2$Mo$_3$O$_8$, a potential positive electrode. While no electrochemical activity is observed, chemical demagnesiation of Mg$_2$Mo$_3$O$_8$ is successful but leads to amorphization. Subsequent first-principles calculations predict a strong thermodynamic driving force for structure decomposition at low Mg concentrations and high activation barriers for bulk Mg diffusion, in agreement with experimental observations. Further analysis of the Mg diffusion pathway reveals an O--Mg--O dumbbell intermediate site that creates a high Mg$^{2+}$ migration barrier, indicating the influence of transition states on setting the magnitude of migration barriers.