Electrochemical characteristics of Ce0.8Gd0.2O1.9|La0.6Sr0.4CoO3-δ + Ce0.8Gd0.2O1.9 half-cell

The analysis of the medium temperature half-cell Ce_0.8Gd_0.2O_1.9|70 wt% La_0.6Sr_0.4CoO_3- (LSCO) + 30 wt % Ce_0.8Gd_0.2O_1.9 (CGO) has been made by electrochemical impedance, cyclic voltammetry and chronoamperometry. The shape of complex impedance plots depends on temperature and cathodic polarisation of the electrode. Nyquist (Z, Z-) plots were fitted by equivalent circuit taking into account the electrolyte properties (at very high frequencies), charge transfer process at grain boundaries (at high frequencies), and medium and low frequency O₂ reduction process at the cathode surface and inside the porous cathode material. Two different time constants have been obtained for the cathode process, i.e. for electroreduction of oxygen. It was found that the addition of CGO into the cathode material (LSCO) only somewhat decreases the surface catalytic activity but the noticeably higher low-frequency resistance (i.e. mainly diffusion-like mass transfer resistance R_D) values at lower temperatures have been calculated. It was found that the mainly bulk diffusion-limited process at T773 K deviates toward the kinetically mixed process (diffusion + charge transfer) with increasing temperature.     

Influence of nanoporous carbon electrode thickness on the electrochemical characteristics of a nanoporous carbon|tetraethylammonium tetrafluoroborate in acetonitrile solution interface

Electrochemical characteristics for the nanoporous carbon|Et₄NBF₄+acetonitrile interface have been studied by cyclic voltammetry and impedance spectroscopy methods. The influence of the electrolyte concentration and thickness of the nanoporous electrode material on the shape of the cyclic voltammetry and impedance curves has been established and the reasons for these phenomena are discussed. A value of zero charge potential, depending slightly on the structure and concentration of the electrolyte, the region of ideal polarizability and other characteristics have been established. The nanoporous nature of the carbon electrodes introduces a distribution of resistive and capacitive elements, giving rise to complicated electrochemical behaviour. Analysis of the complex plane plots shows that the nanoporous carbon|Et₄NBF₄+acetonitrile electrolyte interface can be simulated by an equivalent circuit, in which two parallel conduction paths in the solid and liquid phases are interconnected by the double-layer capacitance in parallel with the complex admittance of the hindered reaction of the charge transfer or of the partial charge transfer (i.e. adsorption stage limited) process. The values of the characteristic frequency depend on the electrolyte concentration and electrode potential, i.e. on the nature of the ions adsorbed at the surface of the nanoporous carbon electrode. The value of the solid state phase resistance established is independent of the thickness of the electrode material.     

Influence of electrolyte characteristics on the electrochemical parameters of electrical double layer capacitors

Electrical double layer capacitors based on ideally polarizable nanoporous carbon electrodes in propylene carbonate with the addition of different 1 M Me₃EtNBF₄, Me₂Et₂NBF₄, MeEt₃NBF₄, Et₄NBF₄, Et₃PrNBF₄ and Et₃BuNBF₄ electrolytes have been tested by cyclic voltammetry, chronoamperometry and electrochemical impedance methods. The limits of ideal polarizability, low-frequency limiting capacitance and series resistance, time constant, Ragone plots (energy density vs. power density dependencies) and other characteristics have been discussed. The influence of the electrolyte molar mass on the electrochemical characteristics of the nanoporous carbon electrode cells has been established. The applicability limits of the Srinivasan and Weidner model have been tested.     

Discrete Galerkin method for Fredholm integro-differential equations with weakly singular kernels

Approximations to a solution and its derivatives of a boundary value problem of an nth order linear Fredholm integro-differential equation with weakly singular or other nonsmooth kernels are determined. These approximations are piecewise polynomial functions on special graded grids. For their finding a discrete Galerkin method and an integral equation reformulation of the boundary value problem are used. Optimal global convergence estimates are derived and an improvement of the convergence rate of the method for a special choice of parameters is obtained. To illustrate the theoretical results a collection of numerical results of a test problem is presented.     

Influence of anion composition and size on the double layer capacitance for Bi(111)|room temperature ionic liquid interface

Cyclic voltammetry and electrochemical impedance spectroscopy have been applied for investigation of electrochemically polished Bi(111) electrode in 1-ethyl-3-methyl imidazolium tris(pentafluoroethyl)trifluorophosphate (EMImFAP), 1-ethyl-3-methyl imidazolium tetracyanoborate (EMImTCB) and 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMImBF₄) ionic liquids. The region of ideal polarizability, series resistance and capacitance, limiting high-frequency and low-frequency capacitances have been calculated. The lower series capacitance values at electrode potential less negative than the potential of the minimum in the capacitance vs. voltage curve for Bi(111)|EMImFAP than that for EMImBF₄, and especially for EMImTCB, have been explained by the bigger diameter of FAP^?, higher cation and anion sizes symmetry, and less expressed surface activity (i.e. lower closest approach of the FAP^? mass centre to an electrode surface) compared with BF₄^? and TCB^? anions.     

Air-coupled ultrasonic assessment of wood veneer

Air-coupled ultrasound (ACU) provides a tool to evaluate wood samples of small or moderate thickness (<30 mm) thereby avoiding direct contact or liquid coupling. Results of through-transmission ACU measurements on wood veneer samples and related products are reported with respect to a wide variety of quality aspects. Fluctuations in the averaged received signal levels appear to be correlated to the presence of natural or machine-induced thickness and density variations, flaws and grain damage, errors produced by the manufacturing process, insufficient bonding on a substrate, etc. In addition it is seen that the variability of the signal levels enables to distinguish between quarter and crown areas.     

Enhanced stability of symmetrical polymer electrolyte membrane fuel cell single cells based on novel hierarchical microporous-mesoporous carbon supports

Fuel cell electrodes were prepared from Pt nanocluster activated hierarchical microporous-mesoporous carbon powders. The carbon supports were synthesized from molybdenum carbide applying the high-temperature chlorination method. Six different synthesis temperatures within the range from 600 to 1000 °C were used for preparation of carbon supports. Thermogravimetric analysis, X-ray diffraction, low-temperature nitrogen sorption, and high-resolution scanning electron microscopy methods were used to characterize the structure of the electrode materials and symmetrical membrane electrode assemblies (MEAs). The MEAs prepared were used to conduct the proton exchange membrane fuel cell (PEMFC)single-cell measurements. The polarization and power density curves for single cells were calculated to evaluate the activity of the catalyst materials synthesized. The electrochemically active surface area (from 2.4 to 11.9 m² g^?1) was obtained in order to estimate the contact surface areas of platinum and Nafion® electrolyte. The values of the electrolyte resistance, polarization resistance, and cell degradation rate were calculated from electrochemical impedance spectroscopy data. The carbon materials synthesized within temperature range from 600 to 850 °C were found to be the most suitable supports for PEMFCs, having higher maximum power density values and better stability (cell potential degradation 240 μV h^?1) than commercial carbon-based (Vulcan XC72; 670 μV h^?1) single cells.