Impedance as a tool for investigating ageing in lithium-ion porous electrodes. Part 1: physically based electrochemical model: I. Physically based electrochemical model

Electrochemical impedance spectroscopy is potentially a powerful diagnostic tool for the investigation of the effects of aging in porous electrodes. A physically based three-electrode model was developed for a Lix Ni0.8 Co0.15 Al0.05 O2 composite porous electrode with three porous separators and a reference electrode between a current collector and a plane electrode. Two effects of aging were modeled for this particular electrode chemistry, namely, a resistive corrosion layer on the current collector and a contact resistance between the electronic conductor and the active material of the porous electrode. The derivation of an analytical solution for the impedances between each pair of electrodes in this model yielded a computationally fast, versatile, and modular formulation. The solution was used to study the impact of selected components of the physical model on the impedance spectrum of the porous electrode for a physically relevant base case. Approximating the active material particles as spherical or flake-shaped particles, lognormally or Dirac distributed in size, revealed that the distribution has a negligible impact while the shape makes a noticeable difference. The main aging-related parameters were shown to have quite distinct effects on the impedance spectrum, which is essential for the regression of experimental data and the study of aging hypotheses.