Bismuth sulfide: A high-capacity anode for sodium-ion batteries

Exploring high-performance anode materials is currently one of the most urgent issues towards practical sodium-ion batteries (SIBs). In this work, Bi2S3 is demonstrated to be a high-capacity anode for SIBs for the first time. The specific capacity of Bi2S3 nanorods achieves up to 658 and 264 mAh g-1 at a current density of 100 and 2000 mA g-1, respectively. A full cell with Na3V2(PO4)3-based cathode is also assembled as a proof of concept and delivers 340 mAh g-1 at 100 mA g-1. The sodium storage mechanism of Bi2S3 is investigated by ex-situ XRD coupled with high-resolution TEM (HRTEM), and it is found that sodium storage is achieved by a combined conversion-intercalation mechanism.

3D Fe2(MoO4)3 microspheres with nanosheet constituents as high-capacity anode materials for lithium-ion batteries

Three-dimensional (3D) Fe2(MoO4)3 microspheres with ultrathin nanosheet constituents are first synthesized as anode materials for the lithium-ion battery. It is interesting that the single-crystalline nanosheets allow rapid electron/ion transport on the inside, and the high porosity ensures fast diffusion of liquid electrolyte in energy storage applications. The electrochemical properties of Fe2(MoO4)3 as anode demonstrates that 3D Fe2(MoO4)3 microspheres deliver an initial capacity of 1855 mAh/g at a current density of 100 mA/g. Particularly, when the current density is increased to 800 mA/g, the reversible capacity of Fe2(MoO4)3 anode still arrived at 456 mAh/g over 50 cycles. The large and reversible capacities and stable charge–discharge cycling performance indicate that Fe2(MoO4)3 is a promising anode material for lithium battery applications. Graphical abstract The electrochemical properties of Fe2(MoO4)3 as anode demonstrates that 3D Fe2(MoO4)3 microspheres delivered an initial capacity of 1855 mAh/g at a current density of 100 mA/g. When the current density was increased to 800 mA/g, the Fe2(MoO4)3 still behaved high reversible capacity and good cycle performance.

A germanium/single-walled carbon nanotube composite paper as a free-standing anode for lithium-ion batteries

Paper-like free-standing germanium (Ge) and single-walled carbon nanotube (SWCNT) composite anodes were synthesized by the vacuum filtration of Ge/SWCNT composites, which were prepared by a facile aqueous-based method. The samples were characterized by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Electrochemical measurements demonstrate that the Ge/SWCNT composite paper anode with the weight percentage of 32% Ge delivered a specific discharge capacity of 417 mA h g-1 after 40 cycles at a current density of 25 mA g-1, 117% higher than the pure SWCNT paper anode. The SWCNTs not only function as a flexible mechanical support for strain release, but also provide excellent electrically conducting channels, while the nanosized Ge particles contribute to improving the discharge capacity of the paper anode.

In-situ one-step hydrothermal synthesis of a lead germanate-graphene composite as a novel anode material for lithium-ion batteries

Lead germanate-graphene nanosheets (PbGeO3-GNS) composites have been prepared by an efficient one-step, in-situ hydrothermal method and were used as anode materials for Li-ion batteries (LIBs). The PbGeO3 nanowires, around 100–200 nm in diameter, are highly encapsulated in a graphene matrix. The lithiation and de-lithiation reaction mechanisms of the PbGeO3 anode during the charge-discharge processes have been investigated by X-ray diffraction and electrochemical characterization. Compared with pure PbGeO3 anode, dramatic improvements in the electrochemical performance of the composite anodes have been obtained. In the voltage window of 0.01–1.50 V, the composite anode with 20 wt.% GNS delivers a discharge capacity of 607 mAh g−1 at 100 mA g−1 after 50 cycles. Even at a high current density of 1600 mA g−1, a capacity of 406 mAh g−1 can be achieved. Therefore, the PbGeO3-GNS composite can be considered as a potential anode material for lithium ion batteries.

Low-temperature plasmas in carbon nanostructure synthesis

Plasma-based techniques offer many unique possibilities for the synthesis of various nanostructures both on the surface and in the plasma bulk. In contrast to the conventional chemical vapor deposition and some other techniques, plasma-based processes ensure high level of controllability, good quality of the produced nanomaterials, and reduced environmental risk. In this work, the authors briefly review the unique features of the plasma-enhanced chemical vapor deposition approaches, namely, the techniques based on inductively coupled, microwave, and arc discharges. Specifically, the authors consider the plasmas with the ion/electron density ranging from 10^10 to 10^14 cm−3, electron energy in the discharge up to ∼10 eV, and the operating pressure ranging from 1 to 10^4 Pa (up to 105 Pa for the atmospheric-pressure arc discharges). The operating frequencies of the discharges considered range from 460 kHz for the inductively coupled plasmas, and up to 2.45 GHz for the microwave plasmas. The features of the direct-current arc discharges are also examined. The authors also discuss the principles of operation of these systems, as well as the effects of the key plasma parameters on the conditions of nucleation and growth of the carbon nanostructures, mainly carbon nanotubes and graphene. Advantages and disadvantages of these plasma systems are considered. Future trends in the development of these plasma-based systems are also discussed.

Control of morphology and nucleation density of iron oxide nanostructures by electric conditions on iron surfaces exposed to reactive oxygen plasmas

The possibility to control the morphology and nucleation density of quasi-one-dimensional, single-crystalline α -Fe2 O3 nanostructures by varying the electric potential of iron surfaces exposed to reactive oxygen plasmas is demonstrated experimentally. A systematic increase in the oxygen ion flux through rf biasing of otherwise floating substrates and then an additional increase of the ion/neutral density resulted in remarkable structural transformations of straight nanoneedles into nanowires with controlled tapering/aspect ratio and also in larger nucleation densities. Multiscale numerical simulations relate the microscopic ion flux topographies to the nanostructure nucleation and morphological evolution. This approach is applicable to other metal-oxide nanostructures.

Suppression of current fluctuations in a crossed E×B field system for low-voltage plasma immersion treatment

Plasma transport in a hybrid dc vacuum arc plasma source for ion deposition and plasma immersion treatment is considered. It is found that external crossed electric and magnetic fields near the substrate can significantly reduce the relative amplitude of ion current fluctuations I-f at the substrate surface. In particular, I-f decreases with the applied magnetic field when the bias voltage exceeds 300 V, thus allowing one to reduce the deviations from the rated process parameters. This phenomenon can be attributed to an interaction between the metal-plasma jet from the arc source and the discharge plasma in the crossed fields. © 2006 American Institute of Physics.

Equilibrium and relaxation of particulate charge in fluorocarbon plasmas

Charging of micron-size particulates, often appearing in fluorocarbon plasma etching experiments, is considered. It is shown that in inductively coupled and microwave slot-excited plasmas of C4F8 and Ar gas mixtures, the equilibrium particle charge and charge relaxation processes are controlled by a combination of microscopic electron, atomic (Ar+ and F+), and molecular ion (CF+ 3, CF+ 2, and CF+) currents. The impact of molecular ion currents on the particulate charging and charge relaxation processes is analyzed. It is revealed that in low-power (<0.5 kW) microwave slot-excited plasmas, the impact of the combined molecular ion current to the total positive microscopic current on the particle can be as high as 40%. The particulate charge relaxation rate in fluorocarbon plasmas appears to exceed 108 s-1, which is almost one order of magnitude higher than that from purely argon plasmas. This can be attributed to the impact of positive currents of fluorocarbon molecular ions, as well as to the electron density fluctuations with particle charge, associated with electron capture and release by the particulates.

Multilevel converter structure and control

In recent years, multilevel converters are becoming more popular and attractive than traditional converters in high voltage and high power applications. Multilevel converters are particularly suitable for harmonic reduction in high power applications where semiconductor devices are not able to operate at high switching frequencies or in high voltage applications where multilevel converters reduce the need to connect devices in series to achieve high switch voltage ratings. This thesis investigated two aspects of multilevel converters: structure and control. The first part of this thesis focuses on inductance between a DC supply and inverter components in order to minimise loop inductance, which causes overvoltages and stored energy losses during switching. Three dimensional finite element simulations and experimental tests have been carried out for all sections to verify theoretical developments. The major contributions of this section of the thesis are as follows: The use of a large area thin conductor sheet with a rectangular cross section separated by dielectric sheets (planar busbar) instead of circular cross section wires, contributes to a reduction of the stray inductance. A number of approximate equations exist for calculating the inductance of a rectangular conductor but an assumption was made that the current density was uniform throughout the conductors. This assumption is not valid for an inverter with a point injection of current. A mathematical analysis of a planar bus bar has been performed at low and high frequencies and the inductance and the resistance values between the two points of the planar busbar have been determined. A new physical structure for a voltage source inverter with symmetrical planar bus bar structure called Reduced Layer Planar Bus bar, is proposed in this thesis based on the current point injection theory. This new type of planar busbar minimises the variation in stray inductance for different switching states. The reduced layer planar busbar is a new innovation in planar busbars for high power inverters with minimum separation between busbars, optimum stray inductance and improved thermal performances. This type of the planar busbar is suitable for high power inverters, where the voltage source is supported by several capacitors in parallel in order to provide a low ripple DC voltage during operation. A two layer planar busbar with different materials has been analysed theoretically in order to determine the resistance of bus bars during switching. Increasing the resistance of the planar busbar can gain a damping ratio between stray inductance and capacitance and affects the performance of current loop during switching. The aim of this section is to increase the resistance of the planar bus bar at high frequencies (during switching) and without significantly increasing the planar busbar resistance at low frequency (50 Hz) using the skin effect. This contribution shows a novel structure of busbar suitable for high power applications where high resistance is required at switching times. In multilevel converters there are different loop inductances between busbars and power switches associated with different switching states. The aim of this research is to consider all combinations of the switching states for each multilevel converter topology and identify the loop inductance for each switching state. Results show that the physical layout of the busbars is very important for minimisation of the loop inductance at each switch state. Novel symmetrical busbar structures are proposed for multilevel converters with diode-clamp and flying-capacitor topologies which minimise the worst case in stray inductance for different switching states. Overshoot voltages and thermal problems are considered for each topology to optimise the planar busbar structure. In the second part of the thesis, closed loop current techniques have been investigated for single and three phase multilevel converters. The aims of this section are to investigate and propose suitable current controllers such as hysteresis and predictive techniques for multilevel converters with low harmonic distortion and switching losses. This section of the thesis can be classified into three parts as follows: An optimum space vector modulation technique for a three-phase voltage source inverter based on a minimum-loss strategy is proposed. One of the degrees of freedom for optimisation of the space vector modulation is the selection of the zero vectors in the switching sequence. This new method improves switching transitions per cycle for a given level of distortion as the zero vector does not alternate between each sector. The harmonic spectrum and weighted total harmonic distortion for these strategies are compared and results show up to 7% weighted total harmonic distortion improvement over the previous minimum-loss strategy. The concept of SVM technique is a very convenient representation of a set of three-phase voltages or currents used for current control techniques. A new hysteresis current control technique for a single-phase multilevel converter with flying-capacitor topology is developed. This technique is based on magnitude and time errors to optimise the level change of converter output voltage. This method also considers how to improve unbalanced voltages of capacitors using voltage vectors in order to minimise switching losses. Logic controls require handling a large number of switches and a Programmable Logic Device (PLD) is a natural implementation for state transition description. The simulation and experimental results describe and verify the current control technique for the converter. A novel predictive current control technique is proposed for a three-phase multilevel converter, which controls the capacitors' voltage and load current with minimum current ripple and switching losses. The advantage of this contribution is that the technique can be applied to more voltage levels without significantly changing the control circuit. The three-phase five-level inverter with a pure inductive load has been implemented to track three-phase reference currents using analogue circuits and a programmable logic device.

Modeling the stepped potential discharge of primary alkaline battery cathodes

A novel model for the potentiostatic discharge of primary alkaline battery cathodes is presented. The model is used to simulate discharges resulting from the stepped potential electrochemical spectroscopy (SPECS) of primary alkaline battery cathodes cathodes, and the results are validated with experimental data. We show that a model based on a single (or mean) reaction framework can be used to simulate multi-reaction discharge behaviour and we develop a consistent functional modification to the kinetic equation of the model that allows for this to occur. The model is used to investigate the effects that the initial exchange current density, i00, and the diffusion coefficient for protons in electrolytic manganese dioxide (EMD), DH+, have on SPECS discharge. The behaviour observed is consistent with the idea that individual reduction reactions, within the multi-reaction, reduction behaviour of EMD, have distinct i00 and DH+ values.

The low-affinity site of the β1-adrenoceptor and its relevance to cardiovascular pharmacology

β-Adrenoceptor blocking agents (β-blockers) that at low concentrations antagonize cardiostimulant effects of catecholamines, but at high concentrations also cause cardiostimulation, have been appearing since the late 1960s. These cardiostimulant β-blockers, coined non-conventional partial agonists, antagonize the effects of catecholamines through a high-affinity site (β1HAR), but cause cardiostimulation mainly through a low-affinity site (β1LAR) of the myocardial β1-adrenoceptor. The experimental non-conventional partial agonist (−)-CGP12177 increases cardiac L-type Ca2+ current density and Ca2+ transients, shortens action potential duration but augments action potential plateau, increases heart rate and force, as well as causes arrhythmic Ca2+ transients and arrhythmic cardiocyte contractions. Other β-blockers, which do not cause cardiostimulation, consistently have lower affinity for β1LAR than β1HAR. These sites were verified and the cardiac pharmacology of non-conventional partial agonists confirmed on recombinant β1-adrenoceptors and on β1-adrenoceptors overexpressed into the heart. A targeted mutation of Asp138 to Glu138 virtually abolished the pharmacology of β1HAR but left intact the pharmacology of β1LAR. Non-conventional partial agonists may be beneficial for the treatment of peripheral autonomic neuropathy but probably due to their arrhythmic propensities, may be harmful for the treatment of chronic heart failure.

Thermal stability of the soil minerals destinezite and diadochite Fe3+2(PO4)(SO4)(OH)·6H2O - implications for soils in bush fires

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the soil minerals destinezite and diadochite. These two minerals are identical except for their morphology. Diadochite is amorphous whereas destinezite is crystalline. Both minerals are found in soils. It is important to understand the stability of these minerals because soils are subject to bush fires especially in Australia. The thermal analysis patterns of the two minerals are similar but not identical. Subtle differences are observed in the DTG patterns. For destinezite, two DTG peaks are observed at 129 and 182°C attributed to the loss of hydration water, whereas only a broad peak with maximum at 84°C is observed for diadochite. Higher temperature mass losses at 685°C for destinezite and 655°C for diadochite, based upon the ion current curves, are due to sulphate decomposition. This research has shown that at low temperatures the minerals are stable but at high temperatures, as might be experienced in a bush fire, the minerals decompose.

Thermal stability of the ‘cave’ mineral brushite CaHPO4•2H2O -mechanism of formation and decomposition

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the ‘cave’ mineral brushite. X-ray diffraction shows that brushite from the Jenolan Caves is very pure. Thermogravimetric analysis coupled with ion current mass spectrometry shows a mass loss at 111°C due to loss of water of hydration. A further decomposition step occurs at 190°C with the conversion of hydrogen phosphate to a mixture of calcium ortho-phosphate and calcium pyrophosphate. TG-DTG shows the mineral is not stable above 111°C. A mechanism for the formation of brushite on calcite surfaces is proposed, and this mechanism has relevance to the formation of brushite in urinary tracts.

Pharmacological consequence of the A118G μ opioid receptor polymorphism on morphine-and fentanyl-mediated modulation of Ca2+ channels in humanized mouse sensory neurons

Background: The most common functional single nucleotide polymorphism of the human OPRM1 gene, A118G, has been shown to be associated with interindividual differences in opioid analgesic requirements, particularly with morphine, in patients with acute postoperative pain. The purpose of this study was to examine whether this polymorphism would modulate the morphine and fentanyl pharmacological profile of sensory neurons isolated from a humanized mouse model homozygous for either the 118A or 118G allele. Methods: The coupling of wild-type and mutant μ opioid receptors to voltage-gated Ca channels after exposure to either ligand was examined by employing the whole cell variant of the patch-clamp technique in acutely dissociated trigeminal ganglion neurons. Morphine-mediated antinociception was measured in mice carrying either the 118AA or 118GG allele. RESULTS:: The biophysical parameters (cell size, current density, and peak current amplitude potential) measured from both groups of sensory neurons were not significantly different. In 118GG neurons, morphine was approximately fivefold less potent and 26% less efficacious than that observed in 118AA neurons. On the other hand, the potency and efficacy of fentanyl were similar for both groups of neurons. Morphine-mediated analgesia in 118GG mice was significantly reduced compared with the 118AA mice. Conclusions: This study provides evidence to suggest that the diminished clinical effect observed with morphine in 118G carriers results from an alteration of the receptor's pharmacology in sensory neurons. In addition, the impaired analgesic response with morphine may explain why carriers of this receptor variant have an increased susceptibility to become addicted to opioids. © 2011 the American Society of Anesthesiologists, Inc. Lippincott Williams & Wilkins. Anesthesiology.