Roles of additives in the trihexyl(tetradecyl) phosphonium chloride ionic liquid electrolyte for primary mg-air cells

As reported previously, water saturated trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]) ionic liquid (IL) is a promising electrolyte for magnesium-air batteries. The added water plays an important role in enabling high rate and high efficiency Mg dissolution while stabilizing the Mg interphase. In this work, the role of the water was investigated by replacement with other additives such as toluene and tetrahydrofuran to specifically target the assumed roles of water, namely: (i) enhancement of transport properties; (ii) complexation and stabilization of the Mg anode; (iii) provision of active protons for the cathodic reaction. Discharge tests show that ethylene glycol supports comparable performance to that provided by water. Examination of the viscosity and conductivity of different [P6,6,6,14][Cl]/additive mixtures indicates that a simple consideration of solution characteristics cannot explain the observed trends. Rather, other factors, such as the presence of active protons and/or oxygen-donor groups, are also key features for the development of IL electrolytes for practical magnesium-air cells. Finally, the presence of ethylene glycol in the electrolyte results in a complex gel on the Mg interface, similar to that found in the presence of water. This may also play a role in enabling stable discharge of the Mg anode. © 2014 The Electrochemical Society.

Ionic liquid electrolytes in mg-air batteries

 This study investigated ionic liquid electrolytes for Mg-air batteries and proposed a promising electrolyte material for this battery system. Mg-air batteries employing the proposed material has also shown its promise in energy storage applications.

Biocompatible ionic liquid-biopolymer electrolyte-enabled thin and compact magnesium-air batteries.

With the surge of interest in miniaturized implanted medical devices (IMDs), implantable power sources with small dimensions and biocompatibility are in high demand. Implanted battery/supercapacitor devices are commonly packaged within a case that occupies a large volume, making miniaturization difficult. In this study, we demonstrate a polymer electrolyte-enabled biocompatible magnesium-air battery device with a total thickness of approximately 300 μm. It consists of a biocompatible polypyrrole-para(toluene sulfonic acid) cathode and a bioresorbable magnesium alloy anode. The biocompatible electrolyte used is made of choline nitrate (ionic liquid) embedded in a biopolymer, chitosan. This polymer electrolyte is mechanically robust and offers a high ionic conductivity of 8.9 × 10(-3) S cm(-1). The assembled battery delivers a maximum volumetric power density of 3.9 W L(-1), which is sufficient to drive some types of IMDs, such as cardiac pacemakers or biomonitoring systems. This miniaturized, biocompatible magnesium-air battery may pave the way to a future generation of implantable power sources.

The influence of water and metal ions on the transport properties of Trihexyl(tetradecyl)phosphonium chloride

A recent study indicated that the water-saturated ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P_6,6,6,14][Cl]) provided a viable electrolyte for a Mg-air battery. However, there is limited literature on the properties of IL-water mixtures as battery electrolytes. The physical properties of [P_6,6,6,14][Cl] were studied with the addition of both water and metal salts (M_gCl₂ and LiCl) using conductivity and self-diffusion coefficient measurements. The conductivity of the samples at low water concentrations is surprisingly enhanced by the addition of the metal salt, contrary to lithium IL electrolytes. It was also found that the conductivity of the IL was increased by an order of magnitude by saturation with water. NMR diffusion measurements were used to probe the behaviour of both the cation and the water in the mixtures. It was found that the addition of metal salts to the water-saturated [P_6,6,6,14][Cl] did not affect the transport properties of the water or cation.

Phase equilibria at sub-solidus conditions in the Fe-Mg-Zn-O system in air

The phase equilibria in the Fe-Mg-Zn-O system in the temperature range 1100-1550degreesC in air have been experimentally studied using equilibration and quenching followed by electron probe X-ray microanalysis. The compositions of condensed phases in equilibrium in the binary MgO-ZnO system and the ternary Fe-Mg-O system have been reported at sub-solidus in air. Pseudo-ternary sections of the quaternary Fe-Mg-Zn-O system at 1100, 1250 and 1400degreesC in air were constructed using the experimental data. The solid solution of iron oxide, MgO and ZnO in the periclase (Mg, Zn, Fe)O, spinel (Mg2+, Fe2+, Zn2+)(x)Fe(2+y)3+O4 and zincite (Zn, Mg, Fe)O phases were found to be extensive under the conditions investigated. A continuous spinel solid solution is formed between the magnesioferrite (Mg2+, Fe2+)(x)Fe(2+y)3+O4 and franklinite (Zn2+, Fe2+)(x)Fe(2+y)3+O4 end-members at 1100 and 1250degreesC, extending to magnetite (Fe2+)(x)Fe(2+y)3+O4 at 1400degreesC in air. The compositions along the spinel boundaries were found to be non-stoichiometric, the magnitude of the non-stoichiometry being a function of composition and temperature in air. It was found that hematite dissolves neither MgO nor ZnO in air.

Randomised, double blind, placebo-controlled trial of Echinacea supplementation in air travellers

Objective. To identify whether a standardised Echinacea formulation is effective in the prevention of respiratory and other symptoms associated with long-haul flights. Methods. 175 adults participated in a randomised, double-blind placebo-controlled trial travelling back from Australia to America, Europe, or Africa for a period of 1–5 weeks on commercial flights via economy class. Participants took Echinacea (root extract, standardised to 4.4 mg alkylamides) or placebo tablets. Participants were surveyed before, immediately after travel, and at 4 weeks after travel regarding upper respiratory symptoms and travel-related quality of life. Results. Respiratory symptoms for both groups increased significantly during travel (

A new magnesium-air cell for long-life applications

A novel type of magnesium-air primary cell has been evolved which employs non-polluting and abundantly available materials. The cell is based on the scheme Mg/Mg(NO3)2, NaNO2, H20/Q(C). The magnesium anode utilization is about 90% at a current density of 20 mAcm -2. The anode has been shown to exhibit a low open-circuit corrosion, a relatively uniform pattern of corrosion and a low negative difference effect in the electrolyte developed above as compared to the conventional halide or perchlorate electrolytes. In the usual air-depolarized mode of operation, the cell has been found to be capable of continuous discharge over several months at a constant cell voltage of about 1 V and a current density of 1 mAcm -2 at the cathode. The long service-life capability arises from the formation of a protective film on the porous carbon cathode and fast sedimentation of the anodic product (magnesium hydroxide) in the electrolyte. The cell has a shelf-life in the activated state of about a year due to the low open-circuit corrosion of the anode. These favourable features suggest the practical feasibility of developing economical, long-life, non-reserve magnesium-air ceils for diverse applications using magnesium anodes with a high surface area and porous carbon-air electrodes.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Effect of pouring temperature on cooling slope casting of semi-solid Al-Si-Mg alloy

Present trend of semi-solid processing is directed towards rheocasting route which allows manufacturing of near-net-shape cast components directly from the prepared semi-solid slurry. Generation of globular equi-axed grains during solidification of rheocast components, compared to the columnar dendritic structure of conventional casting routes, facilitates the manufacturing of components with improved mechanical properties and structural integrity. In the present investigation, a cooling slope has been designed and indigenously fabricated to produce semi solid slurry of Al-Si-Mg (A356) alloy and successively cast in a metallic mould. The scope of the present work discusses about development of a numerical model to simulate the liquid metal flow through cooling slope using Eulerian two-phase flow approach and to investigate the effect of pouring temperature on cooling slope semi-solid slurry generation process. The two phases considered in the present model are liquid metal and air. Solid fraction evolution of the solidifying melt is tracked at different locations of the cooling slope, following Schiel's equation. The continuity equation, momentum equation and energy equation are solved considering thin wall boundary condition approach. During solidification of the liquid metal, a modified temperature recovery scheme has been employed taking care of the latent heat release and change of fraction of liquid. The results obtained from simulations are compared with experimental findings and good agreement has been found.

Dissolved oxygen and O-2 flux across the water-air interface of the Changjiang Estuary in May 2003

The field observation of this study was carried out in the Changjiang Estuary from May 19 to 26,2003, just a few days before the Three Gorges Dam began to store water. A total of 29 stations, including 2 anchor stations, were distributed through almost the whole salinity gradient Based on the data gained from these stations, the biogeochemical characteristics of dissolved oxygen (DO) were examined. Spatial distribution of DO concentrations showed the pattern that it increased in a downriver direction. DO concentration generally varied within a narrow range of 733-8.10 mg l(-1) in the freshwater region and the west part of the mixed water region, and after that it increased rapidly. In vertical direction, the differences in DO concentrations between surface and 2 m above the bottom were big at the stations with water depths exceeding 20 m; DO concentration up to 14.88 mg l(-1) was recorded at the sea surface, while at 2 m above the bottom its concentration was only about 4 mg l(-1). The fluctuation in DO concentrations was small during a period of 48 h in the mixed water region and 2 m above the bottom of the seawater region; while it was large during the same period in the seawater region for surface and 5 m below the surface layer, and a maximum variation from 8.77 to 12.66 mg l(-1) in 4 h was recorded. Oxygen fluxes also showed a marked spatio-temporal variation. As a whole, the freshwater region and mixed water region were an oxygen sink while the seawater region was a source. Relationships between dissolved oxygen and some biogeochemical parameters which could markedly influence its spatio-temporal distribution were discussed in this paper. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis of protective Mo-Si-B coatings in molten salts and their oxidation behavior in an air-water mixture

The formation of various phases during boronizing of silicided molybdenum substrates (MoSi2/Mo) was investigated. Boronizing treatments were conducted in molten salts under an inert gas atmosphere in the 700-1000 degrees C temperature range for 3-7 h. Depending on the process type (non-current or electrochemical) and molten salt temperature, the formation of different boride phases (MoB, Mo2B5, MoB2, MoB4) was observed. At the same time, substantial oxidation of the bulk molybdenum disilicide phase (MoSi2) to the Mo5Si3 phase was observed in non-current boronizing. The oxidation resistance of the coatings was investigated by the weight change in an air-water (2.3 vol.%) mixture at a temperature of 500 degrees C for a period up to 700 h. Results indicated that a two-phase microstructure consisting of the MoSi2, matrix phase with 12-15 wt.% of the MoB4 phase greatly improved the oxidation resistance of the molybdenum substrates. The weight gain rate observed was 6.5 center dot 10(-4) mg/cm(2) h. (c) 2006 Elsevier B.V. All rights reserved.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO2 (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 g l(-1); whiled the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure. oxygen, an optimal flow rate was observed at 300 nil min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 ( +/-0.6) kJ mol(-1). (C) 2003 Elsevier Science Ltd. All rights reserved.