Electrical and Thermal Conductivities of Single CuxO Nanowires.

Copper oxide nanowires (NWs) are promising elements for the realization of a wide range of devices for low-power electronics, gas sensors, and energy storage applications, due to their high aspect ratio, low environmental impact, and cost-effective manufacturing. Here, we report on the electrical and thermal properties of copper oxide NWs synthetized through thermal growth directly on copper foil. Structural characterization revealed that the growth process resulted in the formation of vertically aligned NWs on the Cu growth substrate, while the investigation of chemical composition revealed that the NWs were composed of CuO rather than Cu2O. The electrical characterization of single-NW-based devices, in which single NWs were contacted by Cu electrodes, revealed that the NWs were characterized by a conductivity of 7.6 × 10-2 S∙cm-1. The effect of the metal-insulator interface at the NW-electrode contact was analyzed by comparing characterizations in two-terminal and four-terminal configurations. The effective thermal conductivity of single CuO NWs placed on a substrate was measured using Scanning Thermal Microscopy (SThM), providing a value of 2.6 W∙m-1∙K-1, and using a simple Finite Difference model, an estimate for the thermal conductivity of the nanowire itself was obtained as 3.1 W∙m-1∙K-1. By shedding new light on the electrical and thermal properties of single CuO NWs, these results can be exploited for the rational design of a wide range of optoelectronic devices based on NWs.

Binder Free and Flexible Asymmetric Supercapacitor Exploiting Mn3O4 and MoS2 Nanoflakes on Carbon Fibers.

Emerging technologies, such as portable electronics, have had a huge impact on societal norms, such as access to real time information. To perform these tasks, portable electronic devices need more and more accessories for the processing and dispensation of the data, resulting in higher demand for energy and power. To overcome this problem, a low cost high-performing flexible fiber shaped asymmetric supercapacitor was fabricated, exploiting 3D-spinel manganese oxide Mn3O4 as cathode and 2D molybdenum disulfide MoS2 as anode. These asymmetric supercapacitors with stretched operating voltage window of 1.8 V exhibit high specific capacitance and energy density, good rate capability and cyclic stability after 3000 cycles, with a capacitance retention of more than 80%. This device has also shown an excellent bending stability at different bending conditions.

A Facile and Green Synthesis of a MoO2-Reduced Graphene Oxide Aerogel for Energy Storage Devices.

A simple, low cost, and "green" method of hydrothermal synthesis, based on the addition of l-ascorbic acid (l-AA) as a reducing agent, is presented in order to obtain reduced graphene oxide (rGO) and hybrid rGO-MoO2 aerogels for the fabrication of supercapacitors. The resulting high degree of chemical reduction of graphene oxide (GO), confirmed by X-Ray Photoelectron Spectroscopy (XPS) analysis, is shown to produce a better electrical double layer (EDL) capacitance, as shown by cyclic voltammetric (CV) measurements. Moreover, a good reduction yield of the carbonaceous 3D-scaffold seems to be achievable even when the precursor of molybdenum oxide is added to the pristine slurry in order to get the hybrid rGO-MoO2 compound. The pseudocapacitance contribution from the resulting embedded MoO2 microstructures, was then studied by means of CV and electrochemical impedance spectroscopy (EIS). The oxidation state of the molybdenum in the MoO2 particles embedded in the rGO aerogel was deeply studied by means of XPS analysis and valuable information on the electrochemical behavior, according to the involved redox reactions, was obtained. Finally, the increased stability of the aerogels prepared with l-AA, after charge-discharge cycling, was demonstrated and confirmed by means of Field Emission Scanning Electron Microscopy (FESEM) characterization.

Li+ Insertion in Nanostructured TiO2 for Energy Storage.

Nanostructured materials possess unique physical-chemical characteristics and have attracted much attention, among others, in the field of energy conversion and storage devices, for the possibility to exploit both their bulk and surface properties, enabling enhanced electron and ion transport, fast diffusion of electrolytes, and consequently high efficiency in the electrochemical processes. In particular, titanium dioxide received great attention, both in the form of amorphous or crystalline material for these applications, due to the large variety of nanostructures in which it can be obtained. In this paper, a comparison of the performance of titanium dioxide prepared through the oxidation of Ti foils in hydrogen peroxide is reported. In particular, two thermal treatments have been compared. One, at 150 °C in Ar, which serves to remove the residual hydrogen peroxide, and the second, at 450 °C in air. The material, after the treatment at 150 °C, results to be not stoichiometric and amorphous, while the treatment at 450 °C provide TiO2 in the anatase form. It turns out that not-stoichiometric TiO2 results to be a highly stable material, being a promising candidate for applications as high power Li-ion batteries, while the anatase TiO2 shows lower cyclability, but it is still promising for energy-storage devices.

New insights on laser-induced graphene electrodes for flexible supercapacitors: tunable morphology and physical properties.

In certain polymers the graphenization of carbon atoms can be obtained by laser writing owing to the easy absorption of long-wavelength radiation, which generates photo-thermal effects. On a polyimide surface this process allows the formation of a nanostructured and porous carbon network known as laser-induced graphene (LIG). Herein we report on the effect of the process parameters on the morphology and physical properties of LIG nanostructures. We show that the scan speed and the frequency of the incident radiation affect the gas evolution, inducing different structure rearrangements, an interesting nitrogen self-doping phenomenon and consequently different conduction properties. The materials were characterized by infrared and Raman spectroscopy, XPS elemental analysis, electron microscopy and electrical/electrochemical measurements. In particular the samples were tested as interdigitated electrodes into electrochemical supercapacitors and the optimized LIG arrangement was tested in parallel and series supercapacitor configurations to allow power exploitation.

Mixed 1T-2H Phase MoS2/Reduced Graphene Oxide as Active Electrode for Enhanced Supercapacitive Performance.

A hybrid aerogel, composed of MoS2 sheets of 1T (distorted octahedral) and 2H (trigonal prismatic) phases, finely mixed with few layers of reduced graphene oxide (rGO) and obtained by means of a facile environment-friendly hydrothermal cosynthesis, is proposed as electrode material for supercapacitors. By electrochemical characterizations in three- and two-electrode configurations and symmetric planar devices, unique results have been obtained, with specific capacitance values up to 416 F g-1 and a highly stable capacitance behavior over 50000 charge-discharge cycles. The in-depth morphological and structural characterizations through field emission scanning electron microscopy, Raman, X-ray photoelectron spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller, and transmission electron microscopy analysis provides the proofs of the unique assembly of such 3D structured matrix. The unpacked MoS2 structure exhibits an excellent distribution of 1T and 2H phase sheets that are highly exposed to interaction with the electrolyte, and so available for surface/near-surface redox reactions, notwithstanding the quite low overall content of MoS2 embedded in the reduced graphene oxide (rGO) matrix. A comparison with other "more conventional" hybrid rGO-MoX2 electrochemically active materials, synthesized in the same conditions, is provided to support the outstanding behavior of the cosynthesized rGO-MoS2.

In situ MoS2 Decoration of Laser-Induced Graphene as Flexible Supercapacitor Electrodes.

Herein, we are reporting a rapid one-pot synthesis of MoS2-decorated laser-induced graphene (MoS2-LIG) by direct writing of polyimide foils. By covering the polymer surface with a layer of MoS2 dispersion before processing, it is possible to obtain an in situ decoration of a porous graphene network during laser writing. The resulting material is a three-dimensional arrangement of agglomerated and wrinkled graphene flakes decorated by MoS2 nanosheets with good electrical properties and high surface area, suitable to be employed as electrodes for supercapacitors, enabling both electric double-layer and pseudo-capacitance behaviors. A deep investigation of the material properties has been performed to understand the chemical and physical characteristics of the hybrid MoS2-graphene-like material. Symmetric supercapacitors have been assembled in planar configuration exploiting the polymeric electrolyte; the resulting performances of the here-proposed material allow the prediction of the enormous potentialities of these flexible energy-storage devices for industrial-scale production.

Nanostructured Pd hydride microelectrodes: in situ monitoring of pH variations in a porous medium.

In this study we report the exceptional potentiometric properties of pH microprobes made with nanostructured palladium hydride microelectrodes and demonstrate their application by monitoring pH variations resulting from a reaction confined in a porous medium. Their potentiometric response was found to be reproducible and stable over several hours but primarily Nernstian over a remarkably wide pH range, including alkaline conditions up to pH 14. Continuous operation was demonstrated by reloading hydrogen at regular intervals to maintain the correct hydride composition thereby alleviating the need for calibration. These properties were validated by detecting pH transients during the carbonation of Ca(OH)2 within a fibrous mesh. Experimental pHs recorded in situ were in excellent agreement with theoretical calculations for the CO2 partial pressures considered. Results also showed that the electrodes were sufficiently sensitive to differentiate between the formation of vaterite and calcite, two polymorphs of CaCO3. These nanostructured microelectrodes are uniquely suited to the determination of pH in highly alkaline solutions, particularly those arising from interfacial reactions at solid and porous surfaces and are thus highly appropriate as pH sensing tips in scanning electrochemical microscopy.

Scanning electrochemical microscopy: using the potentiometric mode of SECM to study the mixed potential arising from two independent redox processes.

This study demonstrates how the potentiometric mode of the scanning electrochemical microscope (SECM) can be used to sensitively probe and alter the mixed potential due to two independent redox processes provided that the transport of one of the species involved is controlled by diffusion. This is illustrated with the discharge of hydrogen from nanostructured Pd hydride films deposited on the SECM tip. In deareated buffered solutions the open circuit potential of the PdH in equilibrium between its ß and α phases (OCP(ß→α)) does not depend on the tip-substrate distance while in aerated conditions it is found to be controlled by hindered diffusion of oxygen. Chronopotentiometric and amperometric measurements at several tip-substrate distances reveal how the flux of oxygen toward the Pd hydride film determines its potential. Linear sweep voltammetry shows that the polarization resistance increases when the tip approaches an inert substrate. The SECM methodology also demonstrates how dissolved oxygen affects the rate of hydrogen extraction from the Pd lattice. Over a wide potential window, the highly reactive nanostructure promotes the reduction of oxygen which rapidly discharges hydrogen from the PdH. The flux of oxygen toward the tip can be adjusted via hindered diffusion. Approaching the substrate decreases the flux of oxygen, lengthens the hydrogen discharge, and shifts OCP(ß→α) negatively. The results are consistent with a mixed potential due to the rate of oxygen reduction balancing that of the hydride oxidation. The methodology is generic and applicable to other mixed potential processes in corrosion or catalysis.