Anomalous Pseudocapacitive Behavior of a Nanostructured, Mixed- Valent Manganese Oxide Film for Electrical Energy Storage

*S Supporting Information ABSTRACT: While pseudocapacitors represent a promising option for electrical energy storage, the performance of the existing ones must be dramatically enhanced to meet today’s ever-increasing demands for many emerging applications. Here we report a nanostructured, mixed-valent manganese oxide film that exhibits anomalously high specific capacitance (∼2530 F/g of manganese oxide, measured at 0.61 A/g in a two-electrode configuration with loading of active materials ∼0.16 mg/cm2) while maintaining excellent power density and cycling life. The dramatic performance enhancement is attributed to its unique mixed-valence state with porous nanoarchitecture, which may facilitate rapid mass transport and enhance surface double-layer capacitance, while promoting facile redox reactions associated with charge storage by both Mn and O sites, as suggested by in situ X-ray absorption spectroscopy (XAS) and density functional theory calculations. The new charge storage mechanisms (in addition to redox reactions of cations) may offer critical insights to rational design of a new-generation energy storage devices