Physical modelling of the slow voltage relaxation phenomenon in lithium-ion batteries

Kirk, Toby L., Please, Colin P. and Jon Chapman, S. (2021) Physical modelling of the slow voltage relaxation phenomenon in lithium-ion batteries. Journal of the Electrochemical Society, 168 (6), [060554]. (doi:10.1149/1945-7111/ac0bf7).

Abstract

In the lithium-ion battery literature, discharges followed by a relaxation to equilibrium are frequently used to validate models and their parametrizations. Good agreement with experiment during discharge is possible using a pseudo-two-dimensional model such as the Doyle-Fuller-Newman (DFN) model. The relaxation portion, however, is typically not well-reproduced, with the relaxation in experiments occurring much more slowly than in models. In this study, using a model that includes a size distribution of the active material particles, we give a physical explanation for the slow relaxation phenomenon. This model, the Many-Particle-DFN (MP-DFN), is compared against discharge and relaxation data from the literature, and optimal fits of the size distribution parameters (mean and variance), as well as solid-state diffusivities, are found using numerical optimization. The voltage after relaxation is captured by careful choice of the current cutoff time, allowing a single set of physical parameters to be used for all C-rates, in contrast to previous studies. We find that the MP-DFN can accurately reproduce the slow relaxation, across a range of C-rates, whereas the DFN cannot. Size distributions allow for greater internal heterogeneities, giving a natural origin of slower relaxation timescales that may be relevant in other, as yet explained, battery behavior.

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Contributors

Author: Toby L. Kirk

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