Potential and Current Distribution in Electrochemical Cells: Interpretation of the Half‐Cell Voltage Measurements as a Function of Reference‐Electrode Location

The effects of electrode resistance and electrochemical polarization on potential measurements made with reference electrodes in various locations are demonstrated for electrodes with full‐width tabs and idealized polarization characteristics. Nonuniform current distribution, which changes during discharge, can lead to complex behavior in the measurements, which would be missed in the overall cell potential. To detect individual electrode polarization and limiting‐electrode behavior during discharge, it is recommended that the reference‐electrode probe be placed between the working electrodes reasonably close to the tabs.