电化学阻抗谱分析方法.pptVIP

Techniques based on concepts of impedance We have discussed ways of studying electrode reactions through large perturbations on the system, for example, potential sweeps, potential steps, or current steps, the electrode is generally driven to a condition far from equilibrium and the response is observed, which is usually a transient signal. Another approach is to perturb the cell with an alternating signal of small magnitude and observe the way in which system follows the perturbation at steady state. Electrochemical Impedance Spectroscopy Review of ac circuits A purely sinusoidal voltage can be expressed as Where ω is the angular frequency, which is 2π times the conventional frequency in hertz. The current lags the voltage, it can be expressed generally as Where φ is a phase angle. Review of ac circuits A pure resistance R, E=IR, where the phase is zero. A pure capacitance C, Where Xc is the capacitive reactance, 1/ωC A comparison of R and Xc shows that Xc must carry dimensions of resistance, but the magnitude of Xc falls with increasing frequency. Electrochemical Impedance Spectroscopy Review of ac circuits Components along the ordinate are assigned as imaginary and along the abscissa are real, thus, we handle these parameters mathematically as “real” or “imaginary”. A voltage E is applied across R and C Where Z=R-jXc, called the impedance. Review of ac circuits The magnitude of Z and phase angle are given by the following, respectively The impedance is a kind of generalized resistance. The phase angle expresses the balance between capacitive and resistance components in the series circuit. For a pure resistance, φ=0; for a pure capacitance, φ=π/2; and for mixtures, intermediate phase angles are observed. Review of ac circuits For impedances in parallel, the inverse of the overall impedance is the sum of the reciprocals of the individual vectors. Sometimes it is advantageous to analyze ac circuits in terms of the admittance, Y, which is the inverse