Ionic liquid electrolytes as a platform for rechargeable metal–air batteries: a perspective

Metal-air batteries are a well-established technology that can offer high energy densities, low cost and environmental responsibility. Despite these favourable characteristics and utilisation of oxygen as the cathode reactant, these devices have been limited to primary applications, due to a number of problems that occur when the cell is recharged, including electrolyte loss and poor efficiency. Overcoming these obstacles is essential to creating a rechargeable metal-air battery that can be utilised for efficiently capturing renewable energy. Despite the first metal-air battery being created over 100 years ago, the emergence of reactive metals such as lithium has reinvigorated interest in this field. However the reactivity of some of these metals has generated a number of different philosophies regarding the electrolyte of the metal-air battery. Whilst much is already known about the anode and cathode processes in aqueous and organic electrolytes, the shortcomings of these electrolytes (i.e. volatility, instability, flammability etc.) have led some of the metal-air battery community to study room temperature ionic liquids (RTILs) as non-volatile, highly stable electrolytes that have the potential to support rechargeable metal-air battery processes. In this perspective, we discuss how some of these initial studies have demonstrated the capabilities of RTILs as metal-air battery electrolytes. We will also show that much of the long-held mechanistic knowledge of the oxygen electrode processes might not be applicable in RTIL based electrolytes, allowing for creative new solutions to the traditional irreversibility of the oxygen reduction reaction. Our understanding of key factors such as the effect of catalyst chemistry and surface structure, proton activity and interfacial reactions is still in its infancy in these novel electrolytes. In this perspective we highlight the key areas that need the attention of electrochemists and battery engineers, in order to progress the understanding of the physical and electrochemical processes in RTILs as electrolytes for the various forms of rechargeable metal-air batteries.

Combined effect of double antireflection coating and reversible molecular doping on performance of few-layer graphene/n-silicon Schottky barrier solar cells

Few-layer graphene films were grown by chemical vapor deposition and transferred onto n-type crystalline silicon wafers to fabricate graphene/n-silicon Schottky barrier solar cells. In order to increase the power conversion efficiency of such cells the graphene films were doped with nitric acid vapor and an antireflection treatment was implemented to reduce the sunlight reflection on the top of the device. The doping process increased the work function of the graphene film and had a beneficial effect on its conductivity. The deposition of a double antireflection coating led to an external quantum efficiency up to 90% across the visible and near infrared region, the highest ever reported for this type of devices. The combined effect of graphene doping and antireflection treatment allowed to reach a power conversion efficiency of 8.5% exceeding the pristine (undoped and uncoated) device performance by a factor of 4. The optical properties of the antireflection coating were found to be not affected by the exposure to nitric acid vapor and to remain stable over time.

Reversible polyelectrolyte capsules as carriers for protein delivery

A reversible drug delivery system based on spontaneous deposition of a model protein into preformed microcapsules has been demonstrated for protein delivery applications. Layer-by-Layer assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) onto polystyrene sulfonate (PSS) doped CaCO3 particles, followed by core removal yielded intact hollow microcapsules having a unique property to induce spontaneous deposition of bovine serum albumin (BSA) at pH below its isoelectric point of 4.8, where it was positively charged. These capsules showed reversible pH dependent open and closed states to fluorescence labeled dextran (FITC-Dextran) and BSA (FITC-BSA). The loading capacity of BSA increased from 9.1 x 10(7) to 2.03 x 10(8) molecules per capsule with decrease in pH from 4.5 to 3.The loading of BSA-FITC was observed by confocal laser scanning microscopy (CLSM), which showed homogeneous distribution of protein inside the capsule. Efficient loading of BSA was further confirmed by atomic force microscopy (AFM) and scanning electron microscopy (SEM).The interior capsule concentration was as high as 209 times the feeding concentration when the feeding concentration was increased from 1 to 10 mg/ml. The deposition was initially controlled by spontaneous loading mechanism at lower BSA concentration followed by diffusion controlled loading at higher concentration; which decreased the loading efficiency from 35% to 7%. Circular dichroism (CD) measurements and Fourier transform infrared spectroscopy (FTIR) confirmed that there was no significant change in conformation of released BSA in comparison with native BSA. The release was initially burst in the first 0.5 h and sustained up to 5 h. The hollow capsules were found to be biocompatible with mouse embryonic fibroblast (MEF) cells during in vitro cell culture studies. Thus these pH sensitive polyelectrolyte microcapsules may offer a promising delivery system for water soluble proteins and peptides. (C) 2010 Elsevier B.V. All rights reserved.

Electrocaloric Effect in 0.85PMN-0.15PT Thin Films Deposited by Pulsed Laser Deposition

The electrocaloric effect (ECE) of 0.85PbMg(1/3)Nb(2/3)O(3-)0.15PbTiO(3) (0.85PMN-0.15PT) thin films deposited on (111) Pt/TiO2/SiO2/Si substrate by pulsed laser deposition (PLD) has been calculated. The reversible adiabatic temperature was calculated indirectly using the Maxwell's relation Delta T = -T/C rho integral(E2)(E1) (partial derivative P/partial derivative T)(sigma,E)dE. Permittivity and P-E measurements show an anomaly at 11 degrees C on heating only. This anomaly previously reported are claimed to arise due to the PNR depolarization upon heating. The absence of this anomaly during cooling suggests that no structural phase transition takes place. A negative electrocaloric effect is observed which is explained by the increase in the entropy term.

Correlation equations for average deposition rate coefficients of nanoparticles in a cylindrical pore

Nanoparticle deposition behavior observed at the Darcy scale represents an average of the processes occurring at the pore scale. Hence, the effect of various pore-scale parameters on nanoparticle deposition can be understood by studying nanoparticle transport at pore scale and upscaling the results to the Darcy scale. In this work, correlation equations for the deposition rate coefficients of nanoparticles in a cylindrical pore are developed as a function of nine pore-scale parameters: the pore radius, nanoparticle radius, mean flow velocity, solution ionic strength, viscosity, temperature, solution dielectric constant, and nanoparticle and collector surface potentials. Based on dominant processes, the pore space is divided into three different regions, namely, bulk, diffusion, and potential regions. Advection-diffusion equations for nanoparticle transport are prescribed for the bulk and diffusion regions, while the interaction between the diffusion and potential regions is included as a boundary condition. This interaction is modeled as a first-order reversible kinetic adsorption. The expressions for the mass transfer rate coefficients between the diffusion and the potential regions are derived in terms of the interaction energy profile. Among other effects, we account for nanoparticle-collector interaction forces on nanoparticle deposition. The resulting equations are solved numerically for a range of values of pore-scale parameters. The nanoparticle concentration profile obtained for the cylindrical pore is averaged over a moving averaging volume within the pore in order to get the 1-D concentration field. The latter is fitted to the 1-D advection-dispersion equation with an equilibrium or kinetic adsorption model to determine the values of the average deposition rate coefficients. In this study, pore-scale simulations are performed for three values of Peclet number, Pe = 0.05, 5, and 50. We find that under unfavorable conditions, the nanoparticle deposition at pore scale is best described by an equilibrium model at low Peclet numbers (Pe = 0.05) and by a kinetic model at high Peclet numbers (Pe = 50). But, at an intermediate Pe (e.g., near Pe = 5), both equilibrium and kinetic models fit the 1-D concentration field. Correlation equations for the pore-averaged nanoparticle deposition rate coefficients under unfavorable conditions are derived by performing a multiple-linear regression analysis between the estimated deposition rate coefficients for a single pore and various pore-scale parameters. The correlation equations, which follow a power law relation with nine pore-scale parameters, are found to be consistent with the column-scale and pore-scale experimental results, and qualitatively agree with the colloid filtration theory. These equations can be incorporated into pore network models to study the effect of pore-scale parameters on nanoparticle deposition at larger length scales such as Darcy scale.

CONTROLLING OF SCHOTTKY-BARRIER HEIGHTS FOR AU/N-GAAS AND TI/N-GAAS WITH HYDROGEN INTRODUCED AFTER METAL-DEPOSITION BY BIAS ANNEALING

Up to now, in most of the research work done on the effect of hydrogen on a Schottky barrier, the hydrogen was introduced into the semiconductor before metal deposition. This letter reports that hydrogen can be effectively introduced into the Schottky barriers (SBs) of Au/n-GaAs and Ti/n-GaAs by plasma hydrogen treatment (PHT) after metal deposition on [100] oriented n-GaAs substrates. The Schottky barrier height (SBH) of a SB containing hydrogen shows the zero/reverse bias annealing (ZBA/RBA) effect. ZBA makes the SBH decrease and RBA makes it increase. The variations in the SBHs are reversible. In order to obtain obvious ZBA/RBA effects, selection of the temperature for plasma hydrogen treatment is important, and it is indicated that 100-degrees-C for Au/n-GaAs and 150-degrees-C for Ti/n-GaAs are suitable temperatures. It is concluded from the analysis of experimental results that only the hydrogen located at or near the metal-semiconductor interface, rather than the hydrogen in the bulk of either the semiconductor or the metal, is responsible for the ZBA/RBA effect on SBH.

Chemical vapour deposition of vanadium oxide thermochromic thin films

Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films – both undoped and doped with tungsten, niobium and gold nanoparticles – which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

Reversible ageing effects in cryogenically cooled infrared filter radiometers

In this paper we report the observation of drifts in the responsivity of cryogenically cooled InSb detector-based infrared filter radiometers which have very strong wavelength dependence. These drifts can result in the increase or decrease of the response of the filter radiometers by over 5%. The origin of these variations was investigated and was shown to arise due to a thin film of ice formed on the multi-layer bandpass filter used to define the spectral response of the filter radiometer. The thin layer of ice interacts with the characteristics of the filter (which itself consists of a number of thin layers) and modifies the filter spectral transmission thus modifying the response of the filter radiometer of which the filter is part of. These observations are particularly relevant to space instruments which use infrared filter radiometers for earth observation. Debris from the spacecraft engines is known to accumulate on cold surfaces of instruments carried on board. The deposition of this debris on cold filters can modify the spectral response of the instruments, which use these filters to define a spectral response. Crown Copyright (c) 2004 Published by Elsevier B.V. All rights reserved.

Glucose biosensor based on multisegment nanowires exhibiting reversible magnetic control

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Solid electrolytes for electrochromic devices based on reversible metal electrodeposition

Air conditioning and lighting costs can be reduced substantially by changing the optical properties of "intelligent windows." The electrochromic devices studied to date have used copper as an additive. Copper, used here as an electrochromic material, was dissolved in an aqueous animal protein-derived gel electrolyte. This combination constitutes the electrochromic system for reversible electrodeposition. Cyclic voltammetry, chronoamperometric and chromogenic analyses indicated that were obtained good conditions of transparency (initial transmittance of 70%), optical reversibility, small potential window (2.1 V), variation of transmittance in visible light (63.6%) and near infrared (20%) spectral regions. Permanence in the darkened state was achieved by maintaining a lower pulse potential (-0.16 V) than the deposition potential (-1.0 V). Increasing the number of deposition and dissolution cycles favored the transmittance and photoelectrochemical reversibility of the device. The conductivity of the electrolyte (10(-3) S/cm) at several concentrations of CuCl2 was determined by electrochemical impedance spectroscopy. A thermogravimetric analysis confirmed the good thermal stability of the electrolyte, since the mass loss detected up to 100 degrees C corresponded to water evaporation and decomposition of the gel started only at 200 degrees C. Micrographic and small angle X-ray scattering analyses indicated the formation of a persistent deposit of copper particles on the ITO. (C) 2012 Elsevier B.V. All rights reserved.

Nanogravimetric study of lead underpotential deposition on selenium thin films as a semiconductor alloy formation procedure

An electrochemical quartz crystal microbalance Au electrode modified with a Se thin film was used to investigate the electrochemical behavior of lead ad-atoms using underpotential deposition (UPD) conditions. A specific quasi-reversible process was observed during the reduction of Pb2+ on Se thin films in perchloric acid media. The charge density of Pb ad-atoms on Se thin film (46.86 mu C cm(-2)) suggests a recovery of 0.1 monolayers, which is in good agreement with EQCM data. The Se thin film can be successfully alloyed with Pb atoms that are deposited by chronoamperometry using time intervals large enough to allow for diffusion toward the inner Se phase. Linear sweep voltammetry combined with EQCM in perchloric acid was used to characterize the amount of Pb absorbed in the Se thin film. These findings offer a new strategy for alloy formation in semiconductor films using UPD as an effective tool to quantify the exact amount of the incorporated metal.

Characterization of legacy organic carbon in a culturally eutrophic lake : the role of the historic carbon deposition in the time course and extent of lake recovery

The time course of lake recovery after a reduction in external loading of nutrients is often controlled by conditions in the sediment. Remediation of eutrophication is hindered by the presence of legacy organic carbon deposits, that exert a demand on the terminal electron acceptors of the lake and contribute to problems such as internal nutrient recycling, absence of sediment macrofauna, and flux of toxic metal species into the water column. Being able to quantify the timing of a lake’s response requires determination of the magnitude and lability, i.e., the susceptibility to biodegradation, of the organic carbon within the legacy deposit. This characterization is problematic for organic carbon in sediments because of the presence of different fractions of carbon, which vary from highly labile to refractory. The lability of carbon under varied conditions was tested with a bioassay approach. It was found that the majority of the organic material found in the sediments is conditionally-labile, where mineralization potential is dependent on prevailing conditions. High labilities were noted under oxygenated conditions and a favorable temperature of 30 °C. Lability decreased when oxygen was removed, and was further reduced when the temperature was dropped to the hypolimnetic average of 8° C . These results indicate that reversible preservation mechanisms exist in the sediment, and are able to protect otherwise labile material from being mineralized under in situ conditions. The concept of an active sediment layer, a region in the sediments in which diagenetic reactions occur (with nothing occurring below it), was examined through three lines of evidence. Initially, porewater profiles of oxygen, nitrate, sulfate/total sulfide, ETSA (Electron Transport System Activity- the activity of oxygen, nitrate, iron/manganese, and sulfate), and methane were considered. It was found through examination of the porewater profiles that the edge of diagenesis occurred around 15-20 cm. Secondly, historical and contemporary TOC profiles were compared to find the point at which the profiles were coincident, indicating the depth at which no change has occurred over the (13 year) interval between core collections. This analysis suggested that no diagenesis has occurred in Onondaga Lake sediment below a depth of 15 cm. Finally, the time to 99% mineralization, the t99, was viewed by using a literature estimate of the kinetic rate constant for diagenesis. A t99 of 34 years, or approximately 30 cm of sediment depth, resulted for the slowly decaying carbon fraction. Based on these three lines of evidence , an active sediment layer of 15-20 cm is proposed for Onondaga Lake, corresponding to a time since deposition of 15-20 years. While a large legacy deposit of conditionally-labile organic material remains in the sediments of Onondaga Lake, it becomes clear that preservation, mechanisms that act to shield labile organic carbon from being degraded, protects this material from being mineralized and exerting a demand on the terminal electron acceptors of the lake. This has major implications for management of the lake, as it defines the time course of lake recovery following a reduction in nutrient loading.

Potentiostatic Reversible Photoelectrochromism: An Effect Appearing in Nanoporous TiO2/Ni(OH)2 Thin Films

In the field of energy saving, finding composite materials with the ability of coloring upon both illumination and change of the applied electrode potential keeps on being an important goal. In this context, chemical bath deposition of Ni(OH)2 into nanoporous TiO2 thin films supported on conducting glass leads to electrodes showing both conventional electrochromic behavior (from colorless to dark brown and vice versa) together with photochromism at constant applied potential. The latter phenomenon, reported here for the first time, is characterized by fast and reversible coloration upon UV illumination. The bleaching kinetics shows first order behavior with respect to the NiIII centers in the film, and an order 1.2 with respect to electrons in the TiO2 film. From a more applied point of view, this study opens up the possibility of having two-mode smart windows showing not only conventional electrochromism but also reversible darkening upon illumination.

Controlled synthesis of poly(neopentyl p-styrene sulfonate) via reversible addition-fragmentation chain transfer polymerisation

The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using RAFT polymerisation has been studied. Selected experimental conditions led to the production of PNSS with variable molecular weights and low dispersities (D{stroke}≤1.50). The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using reversible addition-fragmentation chain transfer polymerisation has been studied under a wide range of experimental conditions. PNSS can be used as an organic-soluble, thermally labile precursor for industrially valuable poly(p-styrene sulfonate), widely employed in technologies such as ionic exchange membranes and organic electronics. The suitability of two different chain transfer agents, three solvents, three different monomer concentrations and two different temperatures for the polymerisation of neopentyl p-styrene sulfonate is discussed in terms of the kinetics of the process and characteristics of the final polymer. Production of PNSS with systematically variable molecular weights and low dispersities (D{stroke} ≤1.50 in all cases) has been achieved using 2-azidoethyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate in anisole at 75°C, with an initial monomer concentration of 4.0molL-1. Finally, a poly(neopentyl p-styrene sulfonate)-b-polybutadiene-b-poly(neopentyl p-styrene sulfonate) (PNSS-b-PBD-b-PNSS) triblock copolymer has been synthesised via azide-alkyne click chemistry. Moreover, subsequent thermolysis of the PNSS moieties generated poly(p-styrene sulfonate) end blocks. This strategy allows the fabrication of amphiphilic copolymer films from single organic solvents without the need for post-deposition chemical treatment.

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.