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Nb2O5 is a Li+ intercalation metal oxide that is of current interest for lithium ion battery electrodes. The electrophoretic deposition (ED) of Nb2O5 thin-films from aqueous, NbOx colloidal solutio...

The influence of hexamethylenetetraamine (HMTA) on the morphology of δ-MnO2 and its properties for electrical energy storage are investigated—specifically for ultrathick δ-MnO2 layers in the micron scale. Planar arrays of gold@δ-MnO2, core@shell nanowires, were prepared by electrodeposition with and without the HMTA and their electrochemical properties were evaluated. HMTA alters the MnO2 in three ways: First, it creates a more open morphology for the MnO2 coating, characterized by “petals” with a thickness of 6 to 9 nm, rather than much thinner δ-MnO2 sheets seen in the absence of HMTA. Second, the electronic conductivity of the δ-MnO2 is increased by an order of magnitude. Third, δ-MnO2 prepared in HMTA shows a (001) interlayer spacing that is expanded by ≈30% possibly accelerating Li transport. The net effect of “HTMA doping” is to dramatically improve high rate performance, culminating in an increase in the specific capacity for the thickest MnO2 shells examined here by a factor of 15 at 100 mV/s.

Recently we demonstrated that symmetric, all Au@δ-MnO2 core@shell nanowire capacitors can achieve cycle stability to 100 000 cycles and beyond in a poly(methyl methacrylate) (PMMA) gel electrolyte. Here we examine the limits of the PMMA gel to confer this extraordinary stability, in terms of the accessible maximum voltage, Vmax, and the thickness of the PMMA gel electrolyte layer. Two conclusions are (1) the PMMA gel permits the Vmax to be increased by 50% from 1.2 V to 1.8 V, allowing the specific energy to be increased 5–6 fold, and (2) the PMMA gel layer thickness can be reduced from 180 μm (previously) to 2 μm while simultaneously utilizing two layers of nanowires and patterning nanowires in each layer at 5× higher density. For this nanowire “sandwich” architecture, a net increase in volumetric capacity of 600× up to 500 mF/cm3 can be achieved while retaining cycle stability to 100 000 cycles.

Ionic transport at the nanoscale features phenomena that are not observed in larger systems. Nonlinear current–voltage curves characteristic of ionic diodes as well as ion selectivity are examples of effects observed at the nanoscale. Many man-made nanopore systems are inspired by biological channels in a cell membrane, thus measurements are often performed in aqueous solutions. Consequently, much less is known about ionic transport in nonaqueous systems, especially in solid-state electrolytes. Here we show ionic transport through single pores filled with gel electrolyte of poly(methyl methacrylate) (PMMA) doped with LiClO4 in propylene carbonate. The system has no liquid interface and the ionic transport occurs through the porous gel structure. We demonstrate that a conically shaped nanopore filled with the gel rectifies the current and works as a solid-state ionic diode.

Palladium (Pd) nanoparticle (NP)-decorated carbon nanotube (CNT) ropes (or CNT@PdNP) are used as the sensing element for hydrogen gas (H2) chemiresistors. In spite of the fact that Pd NPs have a mean diameter below 6 nm and are highly dispersed on the CNT surfaces, CNT@PdNP ropes produce a relative resistance change 20–30 times larger than is observed at single, pure Pd nanowires. Thus, CNT@PdNP rope sensors improve upon all H2 sensing metrics (speed, dynamic range, and limit-of-detection), relative to single Pd nanowires which heretofore have defined the state-of-the-art in H2 sensing performance. Specifically, response and recovery times in air at [H2] ≈ 50 ppm are one-sixth of those produced by single Pd nanowires with cross-sectional dimensions of 40 × 100 nm Pd. The LODH2 is

Solid and gel electrolytes offer significant advantages for cycle stability and longevity in energy storage technologies. These advantages come with trade-offs such as reduced conductivity and ion mobility, which can impact power density in storage devices even at the nanoscale. Here we propose experiments aimed at exploring the ion transport properties of a hybrid electrolyte system of liquid and gel electrolytes with meso and nanoscale components. We focus on single pore systems featuring LiClO4-propylene carbonate and LiClO4-PMMA gel, which are model electrolytes for energy storage devices. We identified conditions at which the systems considered featured rectifying current-voltage curves, indicating a preferential direction of ion transport. The presented ion current rectification suggests different mechanisms arising from the unique hybrid system: (i) PMMA structure imposing selectivity in fully immersed systems and (ii) ionic selectivity linked to ion sourcing from media of different ionic mobility. These mechanisms were observed to interplay with ion transport properties linked to nanopore structure i.e. cylindrical and conical.

We demonstrate reversible cycle stability for up to 200 000 cycles with 94–96% average Coulombic efficiency for symmetrical δ-MnO2 nanowire capacitors operating across a 1.2 V voltage window in a poly(methyl methacrylate) (PMMA) gel electrolyte. The nanowires investigated here have a Au@δ-MnO2 core@shell architecture in which a central gold nanowire current collector is surrounded by an electrodeposited layer of δ-MnO2 that has a thickness of between 143 and 300 nm. Identical capacitors operating in the absence of PMMA (propylene carbonate (PC), 1.0 M LiClO4) show dramatically reduced cycle stabilities ranging from 2000 to 8000 cycles. In the liquid PC electrolyte, the δ-MnO2 shell fractures, delaminates, and separates from the gold nanowire current collector. These deleterious processes are not observed in the PMMA electrolyte.

Solid and gel electrolytes offer significant advantages for cycle stability and longevity in energy storage technologies. These advantages come with trade-offs such as reduced conductivity and ion mobility, which can impact power density in storage devices even at the nanoscale. Here we propose experiments aimed at exploring the ion transport properties of a hybrid electrolyte system of liquid and gel electrolytes with meso and nanoscale components. We focus on single pore systems featuring LiClO

We describe the preparation and properties of a coaxial, three-layer, gold-CdSe-gold nanowire 30 μm in length that functions as a monolithic photodetector. The gold (Au) electrode core of this sandwich structure is prepared using the lithographically patterned nanowire electrodeposition (LPNE) method on a glass surface. A CdSe shell of defined thickness, dCdSe, from 200 to 280 nm is then electrodeposited on this Au nanowire. Finally, a conformal gold layer is electrodeposited on top of the CdSe shell. The two concentric gold electrodes within this architecture measure the photoconductivity of the ultrathin CdSe absorbing layer in the direction orthogonal to the nanowire axis. This architecture enables accelerated response/recovery of the nanowire to light while simultaneously maximizing the photoconductive gain without relinquishing any of the photoresponsive area of a "bare" nanowire. Characterization by scanning electron microscopy (SEM) of focused ion beam (FIB) cross sections together with electron dispersive X-ray spectroscopy (EDS) reveal the distinct core-multishell nanostructure, layer thicknesses, and layer compositions. The position-dependent photoresponse along the axis of the nanowire, probed using a laser spot, shows that the Au nanoshell significantly enhances the photocurrent. The performance of Au-CdSe-Au core-multishell nanowire photodetectors depend sensitively on the thickness of CdSe nanoshell over the range of from 200 nm < dCdSe < 280 nm. The highest performance was obtained for the dCdSe = 250 nm this device, which showed a photoconductive gain of 2172, a responsivity of 209 A·W(-1), a response time of 17 μs, and a recovery time of 96 μs.

Palladium (Pd) nanoparticle (NP)-decorated carbon nanotube (CNT) ropes (or CNT@PdNP) are used as the sensing element for hydrogen gas (H

The influence of hexamethylenetetraamine (HMTA) on the morphology of δ-MnO

A symmetrical hybrid capacitor consisting of interdigitated, horizontal nanowires is described. Each of the 750 nanowires within the capacitor is 2.5 mm in length, consisting of a gold nanowire core (40 × ≈200 nm) encapsulated within a hemicylindrical shell of δ-phase MnO2 (thickness = 60-220 nm). These Au@δ-MnO2 nanowires are patterned onto a planar glass surface using lithographically patterned nanowire electrodeposition (LPNE). A power density of 165 kW/kg and energy density of 24 Wh/kg were obtained for a typical nanowire array in which the MnO2 shell thickness was 68 ± 8 nm. Capacitors incorporating these ultralong nanowires lost ≈10% of their capacity rapidly, during the first 20 discharge cycles, and then retained 90% of their maximum capacity for the ensuing 6000 cycles. The ability of capacitors consisting of ultralong Au@δ-MnO2 nanowires to simultaneously deliver high power and high capacity with acceptable cycle life is demonstrated.

The preparation by electrodeposition of transverse nanowire electroluminescent junctions (tn-ELJs) is described, and the electroluminescence (EL) properties of these devices are characterized. The lithographically patterned nanowire electrodeposition process is first used to prepare long (millimeters), linear, nanocrystalline CdSe nanowires on glass. The thickness of these nanowires along the emission axis is 60 nm, and the width, wCdSe, along the electrical axis is adjustable from 100 to 450 nm. Ten pairs of nickel-gold electrical contacts are then positioned along the axis of this nanowire using lithographically directed electrodeposition. The resulting linear array of nickel-CdSe-gold junctions produces EL with an external quantum efficiency, EQE, and threshold voltage, Vth, that depend sensitively on wCdSe. EQE increases with increasing electric field and also with increasing wCdSe, and Vth also increases with wCdSe and, therefore, the electrical resistance of the tn-ELJs. Vth down to 1.8(±0.2) V (for wCdSe ≈ 100 nm) and EQE of 5.5(±0.5) × 10(-5) (for wCdSe ≈ 450 nm) are obtained. tn-ELJs produce a broad EL emission envelope, spanning the wavelength range from 600 to 960 nm.

Nanowire electrodes for batteries and super-capacitors can produce superior power relative to films of the same materials. But the Achilles Heel of nanowires is their susceptibility to degradation and failure. This is particularly true for materials that employ Faradaic reactions requiring ion insertion/deinsertion for energy storage. Here we describe the preparation of arrays of ultra-long (2.5 mm) Gold@δ-MnO2, core@shell nanowires. Gold@δ-MnO2 nanowires are prepared on glass surfaces using a variant of the Lithographically Patterned Nanowire Electrodeposition process. All nanowire capacitors prpared from these ultra-long nanowires produce state-of-the-art metrics for energy and power in MnO2-based systems, but they demonstrate irreversible capacity loss exceeding 20% in ≈4000 - 8000 cycles. This cycle stability nevertheless represents the state-of-the-art for MnO2 based electrodes. Now we have discovered that the addition of poly(methylmethacrylate)(PMMA) to the propylene carbonate (PC) electrolyte extends cycle stability to 100,000 cycles and beyond. Other energy storage metrics of these systems are not degraded by the PMMA. In this talk, I describe the results of our experiments, and present data on the charactrerization of these Gold@δ-MnO2 nanowire systems in PC electrolyte and PC electrolyte containing PMMA, before and after cycling.

Nanostructured manganese oxide (MnO2) is one of the widely studied materials for electrochemical capacitors because of the high specific surface area and excellent electrochemical properties leading to improved rate capability and enhanced energy/power densities. Most of the research on MnO2 is aimed at improving the capacitance whereas only a few studies are focused on cycling stability of these electrodes. In this work, degradation in capacitance of arrays of gold core nanowire encapsulated within a hemicylindrical shell of MnO2 will be studied. The horizontal nanowire systems provide an excellent platform for analyzing nanowire performance, such as investigations of the mechanisms contributing to degradation and failure in these systems. Ex-situ Raman spectroscopy, X-ray photoelectron spectroscopy and Grazing incidence X-ray diffraction measurements will be performed on the core/shell nanowires to examine various parameters such as nanowire defects, MnO2 dissolution, mechanical electrode failure behind degradation .