Solid–Liquid Interfacial Coordination Chemistry Enables High‐Capacity Ammonium Storage in Amorphous Manganese Phosphate

Abstract Ammonium (NH 4 + ) ion as charge carrier is attracting attention in aqueous batteries. Yet, most NH 4 + host materials are still limited by the relatively low capacities. Here, we fabricated a manganese phosphate (MP‐20) for NH 4 + ion storage. MP‐20 displays a high capacity of 299.6 mAh g −1 at 1 A g −1 in ammonium acetate (NH 4 Ac) electrolyte, outperforming other reported NH 4 + host materials. Spectroscopy studies suggest a new NH 4 + /H + co‐insertion mechanism. We surprisingly discover that the NH 4 Ac electrolyte plays an important role in improving the charge storage capability of the materials. Experimental and computational results indicate acetate ions can form coordination bonds with the Mn atoms, tailoring the electronic structure of the Mn atoms and the surrounding O atoms, and therefore facilitating the NH 4 + storage process. Our findings provide a new NH 4 + host material and propose the important role of the electrolyte‐electrode coordination effect in aqueous ammonium batteries.