Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor

Aqueous ammonium ion hybrid supercapacitor (A-HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low-cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion-assisted surface functionalization is used to increase the ammonium ion storage capacity of an alpha-MoO3 electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH4+ intercalation into layered alpha-MoO3 is not dominant in the A-HSC system; rather, the charge storage mainly depends on the adsorption energy of surface "O" to NH4+. It is further revealed that the hydrogen bond chemistry of the coordination between "O" of surface phosphate ion and NH4+ is the reason for the capacity increase of MoO3. This study not only advances the basic understanding of rechargeable aqueous A-HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.