Impedance interpretation circuits

Impedance measurements were performed in different frequency ranges at open circuit potential for an alkyd coating with titanium dioxide as a mineral pigment in 3% sodium chloride. The most probable impedance equivalent circuit method was considered for data analysis. The interpretation of the impedance spectra permitted the determination of water permeation, the formation of blisters, swelling of the coating, and the loss of adhesion. 17 refs. 

Normally, the impedance plots are fitted to an often-complex equivalent circuit. Mathematically, this means searching for a global solution in R". However, problems arise if a complicated equivalent circuit is found which does not allow physical interpretation. Therefore, it is preferable to run a wide variety of experiments with different samples rather than trying to fit in detail the results of a single measurement in order to analyze the resulting impedance plots. 

In our opinion, the interesting photoresponses described by Dvorak et al. were incorrectly interpreted by the spurious definition of the photoinduced charge transfer impedance [157]. Formally, the impedance under illumination is determined by the AC admittance under constant illumination associated with a sinusoidal potential perturbation, i.e., under short-circuit conditions. From a simple phenomenological model, the dynamics of photoinduced charge transfer affect the charge distribution across the interface, thus according to the frequency of potential perturbation, the time constants associated with the various rate constants can be obtained [156,159-163]. It can be concluded from the magnitude of the photoeffects observed in the systems studied by Dvorak et al., that the impedance of the system is mostly determined by the time constant. 

The impedance data have been usually interpreted in terms of the Randles-type equivalent circuit, which consists of the parallel combination of the capacitance Zq of the ITIES and the faradaic impedances of the charge transfer reactions, with the solution resistance in series [15], cf. Fig. 6. While this is a convenient model in many cases, its limitations have to be always considered. First, it is necessary to justify the validity of the basic model assumption that the charging and faradaic currents are additive. Second, the conditions have to be analyzed, under which the measured impedance of the electrochemical cell can represent the impedance of the ITIES. 

In particular, the coupling between the ion transfer and ion adsorption process has serious consequences for the evaluation of the differential capacity or the kinetic parameters from the impedance data [55]. This is the case, e.g., of the interface between two immiscible electrolyte solutions each containing a transferable ion, which adsorbs specifically on both sides of the interface. In general, the separation of the real and the imaginary terms in the complex impedance of such an ITIES is not straightforward, and the interpretation of the impedance in terms of the Randles-type equivalent circuit is not appropriate [54]. More transparent expressions are obtained when the effect of either the potential difference or the ion concentration on the specific ion adsorption is negli-... 

Further information on this subject can be obtained by frequency response analysis and this technique has proved to be very valuable for studying the kinetics of polymer electrodes. Initially, it has been shown that the overall impedance response of polymer electrodes generally resembles that of intercalation electrodes, such as TiS2 and WO3 (Ho, Raistrick and Huggins, 1980 Naoi, Ueyama, Osaka and Smyrl, 1990). On the other hand this was to be expected since polymer and intercalation electrodes both undergo somewhat similar electrochemical redox reactions, which include the diffusion of ions in the bulk of the host structures. One aspect of this conclusion is that the impedance response of polymer electrodes may be interpreted on the basis of electrical circuits which are representative of the intercalation electrodes, such as the Randles circuit illustrated in Fig. 9.13. The figure also illustrates the idealised response of this circuit in the complex impedance jZ"-Z ) plane. 

Figure 68. Nyquist plots of a charged lithium ion cell, a lithiated graphite/graphite cell, and a delithiated cathode/ cathode symmetrical cell. The inset is an equivalent circuit used for the interpretation of the impedance spectra. (Reproduced with permission from ref 512 (Figure 3). Copyright 2003 Elsevier.)...

EIS data is generally interpreted based on defining an appropriate equivalent circuit model that best fits the acquired data. The elements of the circuit model involve a specific arrangement of resistors, capacitors, and inductors that tacitly represent the physicochemical reality of the device under test. Under these circumstances the numerical value for chemical properties of the system can be extracted by fitting the data to the equivalent circuit model. Impedance measurements are typically described by one of two models ... 

Commercial impedance analyzers offer equivalent circuit interpretation software that greatly simplifies the interpretation of results. In this Appendix we show two simple steps that were encountered in Chapters 3 and 4 and that illustrate the approach to the solution of equivalent electrical circuits. First is the conversion of parallel to series resistor/capacitor combination (Fig. D.l). This is a very useful procedure that can be used to simplify complex RC networks. Second is the step for separation of real and imaginary parts of the complex equations. 

The interpretation of measured data for Z(oi) is carried out by their comparison with predictions of a theoretical model based either on the (analytical or numerical) integration of coupled charge-transport equations in bulk phases, relations for the interfacial charging and the charge transfer across interfaces, balance equations, etc. Another way of interpretation is to use an -> equivalent circuit, whose choice is mostly heuristic. Then, its parameters are determined from the best fitting of theoretically calculated impedance plots to experimental ones and the results of this analysis are accepted if the deviation is sufficiently small. This analysis is performed for each set of impedance data, Z(co), measured for different values of external parameters of the system bias potentials, bulk concentrations, temperature... The equivalent circuit is considered as appropriate for this system if the parameters of the elements of the circuit show the expected dependencies on the external parameters. 

Transmission line — This term is related to a more general concept of electric -> equivalent circuits used frequently for interpretation of experimental data for complex impedance spectra (-> electrochemical impedance spectroscopy). While the complex -> impedance, Z, at a fixed frequency can always by obtained as a series or parallel combinations of two basic elements, a resistance and a capacitance, it is a much more compli-... 

Alternatively, an equally powerful visualization of impedance data involves Bode analysis. In this case, the magnitude of the impedance and the phase shift are plotted separately as functions of the frequency of the perturbation. This approach was developed to analyze electric circuits in terms of critical resistive and capacitive elements. A similar approach is taken in impedance spectroscopy, and impedance responses of materials are interpreted in terms of equivalent electric circuits. The individual components of the equivalent circuit are further interpreted in terms of phemonenological responses such as ionic conductivity, dielectric behavior, relaxation times, mobility, and diffusion. 

The impedance of the skin has been generally modeled by using a parallel resistance/capacitor equivalent circuit (Fig. 4a). The skin s capacitance is mainly attributed to the dielectric properties of the lipid-protein components of the human epidermis [5,8,9,12]. The resistance is associated primarily with the skin s stratum comeum layer [5,8,9,12]. Several extensions to the basic parallel resistor/capacitor circuit model have appeared in the literature [5,8,9,13]. Most involve two modified parallel resistor/capacitor combinations connected in series [5,8,9]. The interpretation of this series combination is that the first parallel resistor/capacitor circuit represents the stratum comeum and the second resistor/capacitor parallel combination represents the deeper tissues [5,8,9]. The modification generally employed is to add another resistance, either in series and/or in parallel with the original parallel resistor/capacitor combination [8,9]. Realize that because all of these circuits contain a capacitance, they will all exhibit a decrease in impedance as the frequency is increased. This is actually what is observed in all impedance measurements of the skin [5,6,8-15]. In addition, note that the capacitance associated with the skin is 10 times less than that calculated for a biological membrane [12]. This... 

The detailed interpretation of data on HTSC electrochemistry obtained until now in both liquid and solid electrolytes is essentially complicated by the same problem -the choice of the equivalent circuit adequately describing the impedance for the nonzero overvoltages. Peck et al. [153] carried out the quantitative treatment of the results for low- and high-frequency regions separately. As mentioned previously, a thorough treatment of complex-plane impedance diagrams was performed for data obtained in solid electrolytes, but only for the equilibrium potential. 

Examples 4.1 and 4.2 illustrate the manner in which the impedance response of complex arrangements of circuit elements can be derived. In addition to providing an intuitive understanding of the response to a sinusoidal input, these simple circuits often form the basis for a preliminary interpretation of impedance results for electrochemical systems. 

The lack of uniqueness of circuit models creates ambiguity when interpreting impedance response using regression analysis. A good fit does not, in itself, validate the model rised. As discussed in Chapter 23, impedance spectroscopy is not a standalone technique. Additional observations are needed to validate a model. 

Numerical solutions have been presented for the impedance response of semiconducting systems that accoimt for the coupled influence of transport and kinetic phenomena, see, e.g., Bonham and Orazem. Simplified electrical-circuit analogues have been developed to account for deep-level electronic states, and a graphical method has been used to facilitate interpretation of high-frequency measurements of capacitance. The simplified approaches are described in the following sections. 

Graphical methods provide a first step toward interpretation and evaluation of impedance data. An outline of graphical methods is presented in Chapter 16 for simple reactive and blocking circuits. The same concepts are applied here for systems that are more typical of practical applications. The graphical techniques presented in this chapter do not depend on any specific model. The approaches, therefore, can provide a qualitative interpretation. Surprisingly, even in the absence of specific models, values of such physically meaningful parameters as the double-layer capacitance can be obtained from high- or low-frequency asymptotes. 

FRA systems are versatile, and they can be controlled to acquire and analyse the data required to construct Mott-Schottky plots, for example. Unfortunately, the ease of use of FRA-fitting software can lead to errors of interpretation that arise from a failure to relate fitting elements to the physical system. Several equivalent circuits may give the same frequency-dependent impedance response. No a priori distinction between degenerate circuits is possible, ft is necessary to study the system response as a function of additional experimental variables (DC voltage, concentration, mass transport conditions etc.) in order to establish whether the circuit elements are related in a predictable way to a model of the physical system. 

EIS measurements can also be carried out under conditions where illumination of the semiconductor generates a photocurrent. The technique is then referred to as photoelectrochemical impedance spectroscopy, PEIS. Interpretation of the results in terms of passive RC circuit elements is no longer appropriate since the system contains a current source. A more satisfactory approach is to relate the impedance response directly to the physical processes responsible for the photocurrent (Ponomarev and Peter, 1995 Peter, 1999 Peter and Vanmaekelbergh, 1999). 

Foster and Schwan s simplified circuit model has been used to interpret single cell impedance measurements [43-45] providing good agreement with experiments. 

Many applications of this strategy are based on extensions of the concepts of impedance developed earlier in this chapter (41-43). However, the excitation waveform is usually an impulse in potential (rather than a periodic perturbation), and a transient current is measured. One records both E t) and i t) as observed functions. Then both are subjected to transformations, and comparisons are made in the frequency domain between E s) and i s). Ratios of the form i s)IE s) are transient impedances, which can be interpreted in terms of equivalent circuits in exactly the fashion we have come to understand. The advantages of this approach are (a) that the analysis of data is often simpler in the frequency domain, (b) that the multiplex advantage applies, and (c) the waveform E(f) does not have to be ideal or even precisely predictable. The last point is especially useful in high-frequency regions, where potentiostat response is far from perfect. Laplace domain analyses have been carried out for frequency components above 10 MHz. 

The imaginary component of the impedance gives a qualitative picture of the changing interfacial capacitance, but the value has to be interpreted from a correctly devised equivalent circuit to obtain the capacitance value. Here we used the simple Randles circuit (Figure 11). The procedure was similar to that used by Wandlowski et al. (30, 31). The total impedance Z of the Randles circuit is... 

More detailed information on the physical structure and electrical properties can be obtained by analysis of the impedance spectra, as presented in Figure 6. An electrical equivalent circuit [resistance-capacitance (RC) circuit] was used by Fare (38) to interpret the capacitance and conductance data of... 

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