Effect of Proton Diffusion, Electron Conductivity, and Charge‐Transfer Resistance on Nickel Hydroxide Discharge Curves

Abstract

Constant‐current discharge curves for the nickel hydroxide electrode are simulated assuming resistances due to diffusion of protons and conduction of electrons through the nickel hydroxide film, and charge‐transfer resistance at the film/electrolyte interface contribute to the polarization losses of the electrode. Good qualitative agreement is observed between the model predictions and experimental discharge curves. The results suggest that polarization losses due to diffusional limitations of protons is a critical factor in determining the characteristics of the discharge curve. Ohmic resistance has a significant effect on the discharge curves at the end of discharge, and charge‐transfer resistance is a minor contributor to the polarization losses. These findings indicate that accurately measuring the diffusion coefficient of protons, the thickness of the hydroxide film, the initial state‐of‐charge, and the electronic conductivity as a function of state‐of‐charge towards the end of discharge are critical in accurately predicting the discharge characteristics of nickel hydroxide. Physical constants which were shown to have minor influence on the discharge curves are the film conductivity at the beginning of discharge, and the exchange current density and cathodic transfer coefficient for the reaction. The time‐dependent, one‐dimensional diffusion equation has been solved analytically which should provide a computationally efficient means of accounting for proton diffusion and variable electronic conductivity in a macrohomogeneous battery model without sacrificing accuracy.