Impedance spectroscopy dependence

This does not imply that this double layer is at its point of zero charge (pzc). On the contrary, as with every other double layer in electrochemistry, there exists for every metal/solid electrolyte combination one and only one UWr value for which this metal/gas double layer is at its point of zero charge. These critical Uwr values can be determined by measuring the dependency onUWR of the double layer capacitance, Cd, of the effective double layer at the metal/gas interface via AC Impedance Spectroscopy as discussed in Chapter 5.7. 

Figure 5 presents the capacitance-frequency dependence from impedance spectroscopy measurements for CS48 and CS15 in acidic and organic medium. In the low frequency region (from ImHz to lOOmHz) nearly a complete penetration of the ions into the pores is allowed and the quite stable values indicate the domination of the capacitive behavior at the electro 1 ytc/carbon interface. All the curves show a typical drop of... 

Electrochemical impedance spectroscopy was used to determine the effect of isomers of 2,5-bis( -pyridyl)-l,3,4-thiadiazole 36 (n 2 or 3) on the corrosion of mild steel in perchloric acid solution <2002MI197>. The inhibition efficiency was structure dependent and the 3-pyridyl gave better inhibition than the 2-pyridyl. X-ray photoelectron spectroscopy helped establish the 3-pyridyl thiadiazoles mode of action toward corrosion. Adsorption of the 3-pyridyl on the mild steel surface in 1M HCIO4 follows the Langmuir adsorption isotherm model and the surface analysis showed corrosion inhibition by the 3-pyridyl derivative is due to the formation of chemisorbed film on the steel surface. 

For capacity measurements, several techniques are applicable. Impedance spectroscopy, lock-in technique or pulse measurements can be used, and the advantages and disadvantages of the various techniques are the same as for room temperature measurements. An important factor is the temperature dependent time constant of the system which shifts e.g. the capacitive branch in an impedance-frequency diagram with decreasing temperature to lower frequencies. Comparable changes with temperature are also observed in the potential transients due to galvanostatic pulses. 

Important electrical informations about OLEDs, such as charge transport, charge injection, carrier mobility, etc., can be obtained from bias-dependent impedance spectroscopy, which in turn provides insight into the operating mechanisms of the OLED [14,15,73,75 78]. Campbell et al. reported electrical measurements of a PLED with a 50-nm-thick emissive layer [75], Marai et al. studied electrical measurement of capacitance-voltage and impedance frequency of ITO/l,4-Mv-(9-anthrylvinyl)-benzene/Al OLED under different bias voltage conditions [76], They found that the current is space-charge limited with traps and the conductivity exhibits power-law frequency dependence. 

The two main techniques for measuring electrode losses are current interrupt and impedance spectroscopy. When applied between cathode and anode, these techniques allow one to separate the electrode losses from the electrolyte losses due to the fact that most of the electrode losses are time dependent, while the electrolyte loss is purely ohmic. The instantaneous change in cell potential when the load is removed, measured using current interrupt, can therefore be associated with the electrolyte. Alternatively, the electrolyte resistance is essentially equal to the impedance at high frequency, measured in impedance spectroscopy. Because current-interrupt is simply the pulse analogue to impedance spectroscopy, the two techniques, in theory, provide exactly the same information. However, because it is difficult to make a perfect step change in the load, we have found impedance spectroscopy much easier to use and interpret. 

Recently, Darowicki [29, 30] has presented a new mode of electrochemical impedance measurements. This method employed a short time Fourier transformation to impedance evaluation. The digital harmonic analysis of cadmium-ion reduction on mercury electrode was presented [31]. A modern concept in nonstationary electrochemical impedance spectroscopy theory and experimental approach was described [32]. The new investigation method allows determination of the dependence of complex impedance versus potential [32] and time [33]. The reduction of cadmium on DM E was chosen to present the possibility of these techniques. Figure 2 illustrates the change of impedance for the Cd(II) reduction on the hanging drop mercury electrode obtained for the scan rate 10 mV s k... 

Pb UPD on Ag(lll) and Ag(lOO) has been studied using X-ray diffraction method, electrochemical impedance spectroscopy, and in situ scanning probe microscopy [272, 286-288]. This process has been reviewed in [265, 270], see Table 2. Both structure and voltammetric behavior are dependent on the Ag(h, k, 1) plane [265, 289]. 

What Is Impedance Spectroscopy The words impedance spectroscopy imply the dependence of impedance on a wavelength and therefore on frequency. The frequency here is not that of an incident light beam, but of an alternative current applied to a cell, and then the question is What is impedance ... 

Cases in which Impedance Spectroscopy Becomes Limited. One might say that if one understands an interface well, the results of Z-to measurements can be readily understood. Of course, the interest is in the other direction, in using Z-to plots when one does not understand the interlace. Then the task is to find an interfacial structure and mechanism (and its resulting equivalent circuit) that provides a Z that is consistent in its dependence on to with the experimental results of the impedance measurement. This requires finding reasonable parameters to fit the value of the C s and R s as a function of to for the individual elements in the various equivalent circuits. If the shape of the calculated Z-to plot can only be made to match experiment by using C s and R s that are physically unreasonable, the proposed structure and the equivalent circuit to match it are not acceptable and another must be tried. 

Impedance spectroscopy is a valuable addition to the range of techniques for the electrical characterisation of materials and components, especially where interfaces (e.g. metallic electrode/cathode or anode materials) are involved. This is particularly so in the case of batteries and fuel cells, the subjects of the most intensive research and development stimulated by the need to develop power sources which reduce dependence on fossil fuels and their damage to the environment (see Section 4.5.1). 

Careful attention has to be given to the purity of the precursors to avoid detrimental effects on conductivity. In a polycrystalline ceramic the conductivities of grain boundaries and bulk contribute to overall conductivity. In the case of polycrystalline YSZ, because of its unusually high intrinsic (bulk) conductivity the grain boundaries are far less conductive than the crystal, typically by a factor of 100. The effect the grain boundaries have on overall conductivity will depend on grain size and, of course, on impurity content (e.g. silica), since impurities tend to concentrate there. It is the effort to understand more of the various contributors to overall conductivity which has led to the application of impedance spectroscopy (see Section 2.7.5). 

Conventional two-electrode dc measurements on ceramics only yield conductivities that are averaged over contributions of bulk, grain boundaries and electrodes. Experimental techniques are therefore required to split the total sample resistance Rtot into its individual contributions. Four-point dc measurements using different electrodes for current supply and voltage measurement can, for example, be applied to avoid the influence of electrode resistances. In 1969 Bauerle [197] showed that impedance spectroscopy (i.e. frequency-dependent ac resistance measurements) facilitates a differentiation between bulk, grain boundary and electrode resistances in doped ZrC>2 samples. Since that time, this technique has become common in the field of solid state ionics and today it is probably the most important tool for investigating electrical transport in and electrochemical properties of ionic solids. Impedance spectroscopy is also widely used in liquid electrochemistry and reviews on this technique be found in Refs. [198 201], In this section, just some basic aspects of impedance spectroscopic studies in solid state ionics are discussed. 

Owing to its extraordinary chemical stability, diamond is a prospective electrode material for use in theoretical and applied electrochemistry. In this work studies performed during the last decade on boron-doped diamond electrochemistry are reviewed. Depending on the doping level, diamond exhibits properties either of a superwide-gap semiconductor or a semimetal. In the first case, electrochemical, photoelectrochemical and impedance-spectroscopy studies make the determination of properties of the semiconductor diamond possible. Among them are the resistivity, the acceptor concentration, the minority carrier diffusion length, the flat-band potential, electron phototransition energies, etc. In the second case, the metal-like diamond appears to be a corrosion-stable electrode that is efficient in the electrosyntheses (e.g., in the electroreduction of hard to reduce compounds) and electroanalysis. Kinetic characteristics of many outer-sphere... 

The impedance spectroscopy is most promising for electrochemical in situ characterization. Many papers have been devoted to the AB5 type MH electrode impedance analysis [15-17]. Prepared pellets with different additives were used for electrochemical measurements and comparing. Experimental data are typically represented by one to three semicircles with a tail at low frequencies. These could be described to the complex structure of the MH electrode, both a chemical structure and porosity [18, 19] and it is also related to the contact between a binder and alloy particles [20]. The author thinks that it is independent from the used electrolyte, the mass of the electrode powder and the preparing procedure of electrode. However, in our case the data accuracy at high frequencies is lower in comparison with the medium frequency region. In the case, the dependence on investigated parameters is small. In Figures 3-5, the electrochemical impedance data are shown as a function of applied potential (1 = -0.35V, 2 = -0.50V and 3 = -0.75V). 

Immittance — In alternating current (AC) measurements, the term immittance denotes the electric -> impedance and/or the electric admittance of any network of passive and active elements such as the resistors, capacitors, inductors, constant phase elements, transistors, etc. In electrochemical impedance spectroscopy, which utilizes equivalent electrical circuits to simulate the frequency dependence of a given elec-trodic process or electrical double-layer charging, the immittance analysis is applied. 

The immittance analysis can be performed using different kinds of plots, including complex plane plots of X vs. R for impedance and B vs. G for admittance. These plots can also be denoted as Z" vs. Z and Y" vs. Y, or Im(Z) vs. Rc(Z), and Im( Y) vs. Re( Y). Another type of general analysis of immittance is based on network analysis utilizing logarithmic Bode plots of impedance or admittance modulus vs. frequency (e.g., log Y vs. logo)) and phase shift vs. frequency ( vs. log co). Other dependencies taking into account specific equivalent circuit behavior, for instance, due to diffusion of reactants in solution, film formation, or electrode porosity are considered in - electrochemical impedance spectroscopy. Refs. [i] Macdonald JR (1987) Impedance spectroscopy. Wiley, New York [ii] Jurczakowski R, Hitz C, Lasia A (2004) J Electroanal Chem 572 355... 

Potentiodynamictechniques— are all those techniques in which a time-dependent -> potential is applied to an - electrode and the current response is measured. They form the largest and most important group of techniques used for fundamental electrochemical studies (see -> electrochemistry), -> corrosion studies, and in -> electroanalysis, -+ battery research, etc. See also the following special potentiodynamic techniques - AC voltammetry, - DC voltammetry, -> cyclic voltammetry, - linear scan voltammetry, -> polarography, -> pulse voltammetry, - reverse pulse voltammetry, -> differential pulse voltammetry, -> potentiodynamic electrochemical impedance spectroscopy, Jaradaic rectification voltammetry, - square-wave voltammetry. 

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