Frequency-domain analysis impedance measured

The methods described in this chapter and this book apply to electrochemical impedance spectroscopy. Impedance spectroscopy should be viewed as being a specialized case of a transfer-function analysis. The principles apply to a wide variety of frequency-domain measurements, including non-electrochemical measurements. The application to generalized transfer-function methods is described briefly with an introduction to other sections of the text where these methods are described in greater detail. Local impedance spectroscopy, a relatively new and powerful electrochemical approach, is described in detail. 

In the absence of instmment-induced correlations, stochastic errors in the frequency-domain are normally distributed. The appearance of a normal distribution of frequency-domain stochastic errors can be regarded to be a consequence of the Central Limit Theorem applied to the methodology used to measure the complex impedance. ° This result validates an essential assumption routinely used during regression analysis of impedance (and other frequency-domain) data. 

Impedance measurements can be made in either the frequency domain with a frequency response analyzer (FRA) or in the time domain using Fourier transformation with a spectrum analyzer. Commercial instrumentation and software is available for these measurements and the analysis of the data. 

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. 

In this work, we perform a sensitivity analysis of selected parameters of a commercial 26650 LiFePO/graphite cell and investigate their effect on the simulated impedance spectrum. Basic values such as layer thickness and particle radii are taken from literature and preceding measurements. The model implemented within the commercial Finite Element Method (FEM) software COMSOL Multiphysics is then solved in the frequency domain. To demonstrate the capabilities of this method, variations in state of charge, particle radius, solid state diffusion coefficient and reaction rate are analysed. These parameters evoke characteristic and also unusual properties of the observed impedance spectrum. 

With increasing interest in time-resolved impedance measurements but also with the demand of parallel measurements, fast methods based on time domain approach move more and more into the focus. Although time and frequency domain are well defined, they are often not clearly presented. Especially, when the impedance spectrum changes with time, a joint analysis in terms of time and frequency dependence is often accompanied by uncertainties in wording. 

A number of other operational problems exist when using the FFT algorithm. The most important of these, as far as electrochemistry is concerned, is due to the inherently nonlinear nature of the system. When Eq. (56) is used to measure the impedance with an arbitrary time domain input function (i.e. not a single-frequency sinusoidal perturbation), then the Fourier analysis will incorrectly ascribe the harmonic responses due to system nonlinearity, to input signal components which may or may not be present at higher frequencies. As a consequence, the measured impedance spectrum may be seriously in error. 

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