Methods for faster estimation of the entropy profile of a lithium-ion battery: A comparison of accelerated potentiometry and the estimation of entropy through thermal signatures

The operating temperature of a lithium-ion battery (LIB) has strong effects on its electrochemical performance, safety, and lifetime. Reliable predictions of cell temperature and heat generation rate are required for the design and thermal management of battery systems. The entropy variation of a LIB has a significant influence on the heat generation and the cell temperature variation, especially at a lower C-rate. Since the entropy is a function of State-of-Charge (SoC), and may change during ageing, the entropy profile may as well be used as an indicator for battery State-of-Health diagnostics. The present experimental methods, such as potentiometric or calorimetric methods, for determining the entropy variation throughout a battery's full SoC window are time-consuming and require specialized equipment with good thermal insulation and instrumentation. Hence, faster and more convenient methods are needed. In this paper, we compare an accelerated potentiometric method with a new entropy characterization method where the entropy profile is extracted from the thermal signature of a LIB during charge and discharge at low C-rates. The accelerated potentiometric method aims to obtain the entropy from thermal cycling while the cell is still not completely relaxed to its stable OCV. The thermal signature method monitors the variations of a cell's outer surface temperature during a low constant current charge or discharge, from which the continuous variation of entropy with SoC can be extracted. The obtained entropy profile was validated through a modeling approach that combines a P2D-electrochemical model for battery operation and a 3D-finite-element model for the thermal behavior during battery operation. Good agreement between the model predictions and experiments was achieved on the temporal variation of the cell's outer surface temperature.