A simple model of ac hopping surface conductivity in ionic liquids

The boundary conditions proposed to discuss the charge exchange taking place in an ionic liquid in contact with non-blocking electrodes are reconsidered in a dynamic situation. Assuming that the variation of the bulk ionic current density depends linearly on the surface value of the ionic current density, the frequency dependence of the phenomenological parameter is determined. The analysis has been performed in the framework where the relaxation times are smaller than a maximum relaxation time τM, and that the response function is independent on the value of the relaxation time. Using simple physical considerations, an expression for the surface conductivity describing the ionic charge exchange at the electrode is obtained. According to our calculations, its frequency dependence is similar to that predicted for the electric conductivity in disordered materials when the mechanism is of the hopping type. From measurements of impedance spectroscopy, by the best fit of the experimental data, the temperature dependence of the hopping time, of the dc surface conductivity, and of the diffusion coefficient are derived. They are in good agreement with the theoretical predictions obtained with the random distribution of surface energy barrier. Keywords: Ionic liquids, Non-blocking electrodes, Electrical impedance spectroscopy, AC hopping surface conductivit

Investigation of the conduction properties of ionic liquid crystal electrolyte used in dye sensitized solar cells

To investigate the conduction properties of ionic liquid crystal electrolytes and to correlate them to their molecular structure, two electrolytes based on imidazolium iodides have been chosen for a comparative study: one ionic liquid crystal (1-dodecy1-3-methylimidazolium iodide) (C12) and one ionic liquid (1-hexyl-3-methylimidazolium iodide) (C6). For the electrical characterization of the samples the electrochemical impedance spectroscopy technique (EIS) has been used in the frequency range 1 MHz divided by 10 mHz. For both electrolytes three frequency domains have been singled out. At large frequencies a hopping mechanism ensures the relative high conductivity of ionic liquids. A good fit of the conductivity data with respect to temperature with a Vogel-Tamman-Fulcher (VTF) equation has been done. The interesting result is that although C12 has a higher viscosity than C6 and thus a smaller conductivity was expected the observed conductivity is actually larger, this fact being attributed to the smectic A liquid crystal order of C12. At medium frequencies and especially at low frequencies the buildup of double layers by the electrodes is well observed. Assuming that in this region (10 Hz divided by 10 mHz) the cell is equivalent to an electric circuit formed by the parallel of a resistance, R-0, and a capacitance, C-0, the simple Debye relaxation model, characterized by one relaxation time, has been modified taking into account the adsorption phenomenon in the Langmuir approximation. A theoretical interpretation of the experimental results based on the double layer model is presented

Improving the Voltammetric Determination of Hg(II): A Comparison Between Ligand-Modified Glassy Carbon and Electrochemically Reduced Graphene Oxide Electrodes

A new thiosemicarbazone ligand was immobilized through a Cu(I)-catalyzed click reaction on the surface of glassy carbon (GC) and electrochemically reduced graphene oxide (GC-ERGO) electrodes grafted with phenylethynyl groups. Using the accumulation at open circuit followed by anodic stripping voltammetry, the modified electrodes showed a significant selectivity and sensibility for Hg(II) ions. A detection limit of 7 nM was achieved with the GC modified electrodes. Remarkably, GC-ERGO modified electrodes showed a significantly improved detection limit (0.8 nM), sensitivity, and linear range, which we attribute to an increased number of surface binding sites and better electron transfer properties. Both GC and GC-ERGO modified electrodes proved their applicability for the analysis of real water samples