Synthesis and electrochemical performance of LiNi0.5Mn1.5O4 spinel compound

Spinel compound LiNi_0.5Mn_1.5O₄ was synthesized by a chemical wet method. Mn(NO₃)₂, Ni(NO₃)₂·6H₂O, NH₄HCO₃ and LiOH·H₂O were used as the starting materials. At first, Mn(NO₃)₂ and Ni(NO₃)₂·6H₂O reacted with NH₄HCO₃ to produce a precursor, then the precursor reacted with LiOH·H₂O to synthesize product LiNi_0.5Mn_1.5O₄. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi_0.5Mn_1.5O₄ had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm². After 50 cycles, the total discharge capacity was above 118 mAh/g.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

The effect of vacuum evaporation plating on phase structure and electrochemical properties of AB5–5 mass% LaMg3 composite alloy

In this paper, Cu, Al and Ni were plated on the AB₅–5 mass% LaMg₃ composite hydrogen storage alloy using a vacuum evaporation plating method. The phase structure and the electrochemical properties were investigated. The X-ray diffraction (XRD) analysis shows that the phase structure is not changed obviously after the plating Cu, Al and Ni on the composites. The electrochemical tests show that maximum discharge capacity, high rate dischargeability (HRD), dischargeability at low temperature and cyclic stability was improved by vacuum evaporation plating Cu, Al and Ni. Maximum of discharge capacity of the AB₅–5 mass% LaMg₃ composite alloy plating Ni can reach 351 mAh/g, which is 3.5% higher than that of the untreated. HRD at I_d = 1200 mA/g of the composite alloy plating Cu is 45.0% of that at 60 mA/g, which is 20.4% higher than the untreated. Discharge capacity of the composite alloy plating Cu at low temperature 233 K is 205 mAh/g, which is 57.3% of that at 298 K, and it is much higher than 36.8% of the untreated composites. The discharge capacity retention of the composite alloy plating Al after 200 cycles is 7.8% higher than the untreated.     

Novel tin-graphite composites as negative electrodes of Li-ion batteries

For the purpose of obtaining an improved performance of the graphite negative electrode of Li-ion batteries, a novel graphite-tin composite has been synthesized by reduction of tin chloride (SnCl₂) with KC₈ in THF medium. This composite contains nano-sized tin particles dispersed on the graphite surface and free tin aggregates. Lithium electrochemical insertion occurs both in graphite and in tin. An experimental reversible specific charge of 489 mA h g⁻¹ is found stable upon cycling. Such a value is lower than the maximum theoretical one of 609 mA h g⁻¹ suggesting that only a part of tin is involved in the lithium insertion/extraction process. This part of active tin responsible for the stable capacity could be that bound to graphite. To the contrary, free tin aggregates could contribute to an extra capacity that decreases upon cycling in relation with the volume changes that occurs during alloying/dealloying.     

Electrochemical capacitance of well-coated single-walled carbon nanotube with polyaniline composites

Well-coated single-walled carbon nanotube (SWNT) with polyaniline (PANI) composite electrodes with good uniformity for electrochemical capacitors are prepared by the polymerization of aniline containing well-dissolved SWNTs. The capacitance properties are investigated with cyclic voltammetry, charge-discharge tests and ac impedance spectroscopy. The composite electrode shows much higher specific capacitance, better power characteristics and is more promising for application in capacitor than pure PANI electrode. The effect and role of SWNT in the composite electrode are also discussed in detail.     

Morphologic study of electrochemically formed lead dioxide

Various electrochemical methods with different conditions were used to prepare lead dioxide (PbO₂). The observation revealed that the morphology of deposited PbO₂ could be controlled by simply changing deposition parameters. Under the condition of oxygen evolution, which dominates the electrode process, uniformly distributed high porous structured PbO₂ was formed. The results indicated that large current density or high potential polarization should be one of the most important and necessary factors for forming high surface area PbO₂ deposit. Only β-PbO₂ was identified by X-ray diffraction measurement for the deposit prepared by present methods and solution. One potential application of this method is to prepare nanoscaled PbO₂ parallel lines.     

Electrodeposition and dissolution of yttrium-hexacyanoferrate layers

The electrodeposition and dissolution of yttrium-hexacyanoferrate [YHCNFe(II)] were investigated by electrochemical quartz crystal microbalance technique (EQCM). The electrodeposition was carried out by potential cycling or stepping from solutions of Y(NO₃)₃ and K₃[Fe^III(CN)₆] of different concentrations. The ratio of the reactants was also varied. No deposition was found in dilute solutions (c < 10⁻³ mol dm⁻³). The increase of concentrations led to an intense deposition of YHCNFe(II) in the course of reduction of [Fe^III(CN)₆]³⁻. At high concentrations of the reactants a coagulation deposition of YHCNFe(III) at open-circuit has also been detected. During the reduction the first phase is the nucleation which requires saturation or oversaturation in respect to the reacting species near the gold surface. The growth phase is much faster than the formation of nuclei, and its rate depends on the concentration and the concentration ratio of the species. The composition of the deposits has been determined by total reflection X-ray fluorescence (TXRF) spectrometry. From the molar ratio of atomic constituents (K, Y and Fe) of the slightly soluble deposit (solubility: 5 × 10⁻⁵ mol dm⁻³) formed after reduction of Fe(III) a formula K_0.46Y_1.18[Fe^II(CN)₆] can be derived. This value is in good accordance with the molar mass calculated from the results of EQCM experiments which also revealed that the deposit contains ca. 2 mol H₂O/mol YHCNFe(II). The solubility of YHCNFe(III) is substantially higher (s = 2 × 10⁻³ mol dm⁻³), and according to the results of TXRF measurements, its composition is Y[Fe^III(CN)₆]. The reoxidation of YHCNFe(II) takes place in two steps. The first one is a partial oxidation which is accompanied by the desorption of K⁺ ions from the layer. During further oxidation a fast dissolution occurs due to the high solubility of YHCNFe(III).     

Characterization of electrodeposited WO3 films and its application to electrochemical wastewater treatment

WO₃ films have been prepared on to IrO₂-coated Ti substrate by cathodic deposition, and as-deposited and annealed films have been characterized using XRD, TEM, Raman and FT-IR spectroscopy. The as-deposited film consists of nanocrystalline, orthorhombic WO₃·H₂O and this phase transforms to amorphous WO₃ by annealing at 250 °C and to monoclinic WO₃ by annealing at and above 350 °C. The as-deposited and annealed films have been used as anodes for electrochemical decomposition of phenol in aqueous solutions with and without chloride ions. The monoclinic WO₃ anodes prepared by annealing at 350 and 400 °C show relatively high electrochemical activity in the chloride-containing solution. In addition, the anodes possess high chemical and physical stabilities: very low dissolution rate of WO₃ during the electrolysis and good adhesion to the substrate. Thus, WO₃ anodes may be promising materials for anodic oxidation of bio-refractory organics in wastewater, although further improvement of electrochemical activity is needed for more effective decrease in total organic carbons in wastewater.     

Influence of activated carbon pore structure on oxygen reduction at catalyst layers supported on rotating disk electrodes

Carbon materials are often used as catalyst supports, and for catalysts in electrodes of a polymer electrolyte fuel cell, carbon black has been used. Recently, it was found, however, that activated carbon could replace carbon black and besides, significantly improve the activity of the electrode catalyst layer for oxygen reduction. In the present study, to optimize the pore structure of activated carbon for further activity improvement, the influence of the pore structure on the activity was investigated using activated carbon of various specific surface areas and mean pore diameters. A catalyst layer was formed from activated carbon loaded with platinum and a polymer electrolyte. The activity of the layer was measured in an oxygen-saturated perchloric acid solution, supporting the layer on a rotating glassy carbon disk electrode. We found that increases in the specific surface area and mean pore diameter increased the activity and that the latter was more effective than the former mainly due to the enhanced mass-transfer in the pores; the catalyst layer formed from activated carbon with the largest mean pore diameter was the most active. Unless pores excessively develop and lose connections between particles, a large pore diameter is therefore desired for the fuel cell electrodes.     

Preliminary evaluation of the anticorrosive properties of aircraft coatings by electrochemical methods

Strict regulations concerning the content of volatile organic compounds (VOCs) and heavy metals (Cr⁶⁺) in aircraft coating systems have increased the economic burden of the United States Air Force (USAF) in the area of coating maintenance. To this end, it is critical to have methods to characterize new coating systems in such a manner that the data can be used to predict accurately and reliably the expected lifetime of the coatings in service. Electrochemical noise method (ENM) and electrochemical impedance spectroscopy (EIS) are two techniques used to monitor extent and rate of corrosion. The USAF is currently employing these methods in order to supplement data acquired from traditional salt-spray methods. ENM and EIS are used to evaluate each component of the coating system and its contribution to corrosion prevention. Preliminary evaluations of an aircraft coating system on aluminum substrate (Al 2024-T3) produces resistance noise values of 10⁶ to 10⁷ Ω/cm². It is hoped that these results will form the basis of coatings that give increased USAF fleet service life and reduction in maintenance manpower and materials costs.