Demystifying the Distribution of Relaxation Times: A Simulation-Based Investigation into the Limits and Possibilities of Interpretation for Lithium-Ion Batteries

Interpreting impedance spectra of electrochemical systems using the distribution of relaxation times analysis remains an incompletely solved task. This study carefully examines various challenges related to the interpretation of resulting distributions of relaxation times using a closed-form lumped Doyle-Fuller-Newman model. First, the physical and phenomenological interpretation of peaks in the distribution of relaxation times are analyzed through a global sensitivity analysis. Second, the assignment of processes to specific ranges of time constants is investigated. Third, the use of half cells for the characterization of full cells is examined, and the clear limitations associated with the use of lithium metal counter electrodes are pointed out. Furthermore, the study provides first insights into the effects of distributed processes such as charge transfer, double-layer effects, and solid-state diffusion. Several prevailing interpretations in the literature are challenged and new insights and guidelines for interpreting distributions of relaxation times are offered. Analysis of simulated, physics-based impedance spectra of LIB using DRT Study of interaction between model parameters and DRT characteristics Assesment of interpretability of electrochemical and transport processes Investigation of influence of lithium metal counterelectrodes in half-cells Evaluation of interpretability of distributed processes