Theoretical Basics of Monitoring the Condition of the Electrodes of Chemical Current Sources by the Method of Electrochemical Impedance Spectroscopy

Abstract

On the basis of the conducted critical review of modern physical models of the porous electrode, it сan be stated that under the conditions of non-uniform mass transfer taking into account the depth of the electrode, it is possible not only to develop new porous electrodes for a certain application, but also to control the state of electrochemical systems as a whole using the non-destructive method of electrochemical impedance spectroscopy. The presence of a macroscopic model of porous electrode allows one to use the integration of parameters over the surface of the electrode and obtain the average values of current, resistance and capacity within the electrode using the method of averaging in the volume ele­ment within the electrode, where porosity is the volume fraction of the void within the element, which is filled with electrolyte solution. This is the theoretical basis for using electrochemical impedance spectroscopy to assess the state of electrodes in electrochemical current sources. To take into account the influence of the aqueous electrolyte, it is possible to use a model taking into account the area of the effective wetted surface, which makes it possib­le to relate the wetting of the electrode pores with the electrolyte solution to the change in electrical conductivity and polarization of the electrode surface. In this case, when usingelectrochemical impedance spectroscopy, it is possible to obtain information about the following changes in primary current sources: 1– the effect of temperature, which leads to a decrease in the areas of the electrode wetted by the electrolyte, which affect the value of the capacity of the DEL, 2 – chemical processes that lead to the destruction of hydrophilic pores and pores with hydrophilic-hydrophobic walls, an increase in the hydrophobic component on the surface of the electrode, 3 – mechanical destruction of the electrodes. The use of models that take into account the geometry of pores makes it possible to obtain correct data for the analysis of the porous surface in the presence of an electrolyte and in cases of gas phase adsorption in presence of closed pores, as well as to use the value of the capacity on the surface of electrodes to assess the state of their performance.