Modeling of the impedance response of porous metal hydride electrodes

Porous metal hydride electrodes of the alloy MmNi3.5–3.7Co0.7–0.8 Mn0.3–0.4Al0.3–0.4 have been characterized by means of impedance spectroscopy. A mathematical model for the impedance response, including effects of diffusion of hydrogen, surface kinetics, conductivity in the metal phase and the solution phase, as well as a continuous, lognormal, particle size distribution, was implemented and fitted to the experimental results by application of a least square fitting routine. The model is based on physical parameters, thus avoiding problems related to the conventional interpretation of impedance spectra in terms of equivalent circuits. Very good agreement between experimental results and model results was obtained for a wide range of frequencies, indicating that physical parameters to a great extent can be determined under realistic operating conditions. The latter was confirmed by independent measurements of the variation in open circuit voltage with respect to the state of charge of the electrode. The model provides an improved methodology for the determination of diffusion coefficients based on electrochemical impedance data. Furthermore, the model can be applied for parametric studies of metal hydride electrodes.