Thermodynamics of Lead-Acid Battery Degradation: Application of the Degradation-Entropy Generation Methodology

This article details a lead-acid battery degradation model based on irreversible thermodynamics, which is then verified experimentally using commonly measured operational parameters. The model combines thermodynamic first principles with the Degradation-Entropy Generation theorem, to relate instantaneous and cyclic capacity fade (loss of useful charge-holding capacity) in the lead-acid battery to the entropy generated via the underlying dissipative physical processes responsible for battery degradation. Equations relating capacity fade to battery cycling are also formulated and verified. To show robustness of the approach, nonlinear data from uncontrolled and severely abusive battery cycling—including overdischarge—was measured and used to verify formulations. A near 100% agreement between the thermodynamic battery model and measurements is achieved. The model also gives rise to new material and design parameters to characterize all lead-acid batteries.