Recharge Kinetics of the Porous Lead Dioxide Electrode: I . The Effect of Structural Changes

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Abstract
The changes in structure and kinetics during charge of the porous electrode have been studied by means of electrochemical and structure characterizing methods. It was found that the potentiostatic charge current after an initial period of growth, due to nucleation and growth of , is proportional to the decreasing amount of remaining lead sulfate. The polarization curves have a Tafel slope of about 60 mV/decade at overvoltages lower than 0.1V and about 180 mV/decade at higher overvoltages. The form of these curves can be explained by a mechanism with two consecutive single‐electron transfer reactions. The results from these specific studies of the positive electrode and charge experiments with complete lead‐acid cells show that the fastest way to charge lead‐acid batteries is to charge at a constant cell voltage of a value just below that which leads to unacceptable gassing rates.
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