Organic‐Inorganic Coupling Strategy: Clamp Effect to Capture Mg²⁺ for Aqueous Magnesium Ion Capacitor

Abstract

The rapid transport kinetics of divalent magnesium ions are crucial for achieving distinguished performance in aqueous magnesium-ion battery-based energy storage capacitors. However, the strong electrostatic interaction between Mg²⁺ with double charges and the host material significantly restricts Mg²⁺ diffusivity. In this study, a new composite material, EDA-Mn₂O_3, with double-energy storage mechanisms comprising an organic phase (ethylenediamine, EDA) and an inorganic phase (manganese sesquioxide) was successfully synthesized via an organic-inorganic coupling strategy. Inorganic-phase Mn₂O₃ serves as a scaffold structure, enabling the stable and reversible intercalation/deintercalation of magnesium ions. The organic phase EDA adsorbed onto the surface of Mn₂O₃ as an elastic matrix, works synergistically with Mn₂O₃, and utilizes bidentate chelating ligands to capture Mg²⁺. The robust coordination effect of terminal biprotonic amine in EDA enhances the structural diversity and specific capacity characteristics of the composite material, as further corroborated by density functional theory (DFT) calculations, ex situ XRD, XPS, and Raman spectroscopy. As expected, the EDA-Mn₂O₃ composite achieved an outstanding specific discharge capacity of 188.97 mAh/g at 0.1 A/g. Additionally, an aqueous magnesium ion capacitor with EDA-Mn₂O₃ serving as the cathode can reach 110.17 Wh/kg, which stands out among the aqueous magnesium ion capacitors that have been reported thus far. The abundant reversible redox sites are ensured by the strategic design concept based on the synergistic structure and composition advantages of organic and inorganic phases. This study aimed to explore the practical application value of organic-inorganic composite electrodes with double-energy storage mechanisms.