Role of structural H$_2$O in intercalation electrodes: the case of Mg in nano-crystalline Xerogel-V$_2$O$_5$

Abstract

Co-intercalation is a potential approach to influence the voltage and mobility with which cations insert in electrodes for energy storage devices. Combining a robust thermodynamic model with first-principles calculations, we present a detailed investigation revealing the important role of H$_2$O during ion intercalation in nano-materials. We examine the scenario of Mg$^{2+}$ and H$_2$O co-intercalation in nano-crystalline Xerogel-V$_2$O$_5$, a potential cathode material to achieve energy density greater than Li-ion batteries. Water co-intercalation in cathode materials could broadly impact an electrochemical system by influencing its voltages or causing passivation at the anode. The analysis of the stable phases of Mg-Xerogel V$_2$O$_5$ and voltages at different electrolytic conditions reveals a range of concentrations for Mg in the Xerogel and H$_2$O in the electrolyte where there is no thermodynamic driving force for H$_2$O to shuttle with Mg during electrochemical cycling. Also, we demonstrate that H$_2$O shuttling with the Mg$^{2+}$ ions in wet electrolytes yields higher voltages than in dry electrolytes. The thermodynamic framework used to study water and Mg$^{2+}$ co-intercalation in this work opens the door for studying the general phenomenon of solvent co-intercalation observed in other complex solvent-electrode pairs used in the Li- and Na-ion chemical spaces.