This study investigates the charge storage mechanism in reduced graphene oxide (rGO) using a combination of cavity micro-electrode, electrochemical quartz crystal microbalance (EQCM), and electrochemical dilatometry (ECD) techniques. The research highlights two distinct regions of charge storage, depending on the cation-carbon interaction. Under high cathodic polarization, significant capacitance enhancement is observed in Zn²⁺ containing electrolytes with minimal volume expansion, attributed to the desolvation of Zn²⁺ ions due to strong electrostatic interactions with rGO. The findings emphasize the importance of ion-electrode interaction strength and cation desolvation in modulating charging mechanisms, offering potential avenues for optimizing capacitive energy storage. The study also discusses the role of confined geometries and the impact of surface functional groups on charge storage, providing insights into the complex dynamics of charge storage in 2D layered materials.This study investigates the charge storage mechanism in reduced graphene oxide (rGO) using a combination of cavity micro-electrode, electrochemical quartz crystal microbalance (EQCM), and electrochemical dilatometry (ECD) techniques. The research highlights two distinct regions of charge storage, depending on the cation-carbon interaction. Under high cathodic polarization, significant capacitance enhancement is observed in Zn²⁺ containing electrolytes with minimal volume expansion, attributed to the desolvation of Zn²⁺ ions due to strong electrostatic interactions with rGO. The findings emphasize the importance of ion-electrode interaction strength and cation desolvation in modulating charging mechanisms, offering potential avenues for optimizing capacitive energy storage. The study also discusses the role of confined geometries and the impact of surface functional groups on charge storage, providing insights into the complex dynamics of charge storage in 2D layered materials.