Lithographically patterned gold/manganese dioxide core/shell nanowires for high capacity, high rate, and high cyclability hybrid electrical energy storage

Abstract

We describe the fabrication of arrays of nanowires on glass in which a gold core nanowire is encapsulated within a hemicylindrical shell of manganese dioxide. Arrays of linear gold (Au) nanowires are first prepared on glass using the lithographically patterned nanowire electrodeposition (LPNE) method. These Au nanowires have a rectangular cross-section with a width and height of ≈200 and 40 nm, respectively, and lengths in the 1 mm to 1 cm range. Au nanowires are then used to deposit MnO 2 by potentiostatic electrooxidation from Mn 2+ solution, forming a conformal, hemicylindrical shell with a controllable diameter ranging from 50 to 300 nm surrounding each Au nanowire. This MnO 2 shell is δ-phase and mesoporous, as revealed by X-ray diffraction and Raman spectroscopy. Transmission electron microscopy (TEM) analysis reveals that the MnO 2 shell is mesoporous (mp-MnO 2), consisting of a network of ≈2 nm fibrils. The specific capacitance, C sp, of arrays of gold:mp-MnO 2 nanowires is measured using cyclic voltammetry. For a mp-MnO 2 shell thickness of 68 ± 3 nm, core:shell nanowires produce a C sp of 1020 ± 100 F/g at 5 mV/s and 450 ± 70 F/g at 100 mV/s. The cycle stability of this C sp, however, is extremely limited in aqueous electrolyte, decaying by >90% in 100 scans, but after oven drying and immersion in dry 1.0 M LiClO 4, acetonitrile, dramatically improved cycle stability is achieved characterized by the absence of C sp fade for 1000 cycles at 100 mV/s. Core:shell nanowires exhibit true hybrid energy storage, as revealed by deconvolution of C sp into insertion and noninsertion components. © 2012 American Chemical Society.