3D porous nanostructures built from 2D δ-MnO2 nanosheets are an environmentally friendly and industrially scalable class of supercapacitor electrode material. While both the electrochemistry and defects of this material have been studied, the role of defects in improving the energy storage density of these materials has not been addressed. In this work, δ-MnO2 nanosheet assemblies with 150 m2 g−1 specific surface area are prepared by exfoliation of crystalline KxMnO2 and subsequent reassembly. Equilibration at different pH introduces intentional Mn vacancies into the nanosheets, increasing pseudocapacitance to over 300 F g−1, reducing charge transfer resistance as low as 3 Ω, and providing a 50% improvement in cycling stability. X-ray absorption spectroscopy and high-energy X-ray scattering demonstrate a correlation between the defect content and the improved electrochemical performance. The results show that Mn vacancies provide ion intercalation sites which concurrently improve specific capacitance, charge transfer resistance and cycling stability.

This work reports the layer-tunnel conversion of porous dehydrated synthetic alkali-free δ-MnO2 analogs prepared by exfoliation, flocculation, and heat treatment of nanosheets derived from highly crystalline potassium birnessite.