Revisiting the Electrochemical Impedance Spectroscopy of Porous Electrodes in Li‐ion Batteries by Employing Reference Electrode

Abstract Electrochemical impedance spectroscopy (EIS), characterized by its non‐destructive and in situ nature, plays a crucial role in comprehending the thermodynamic and kinetic processes occurring within Li‐ion batteries. However, there is a lack of consistent and coherent physical interpretations for the EIS of porous electrodes. Therefore, it is imperative to conduct thorough investigations into the underlying physical mechanisms of EIS. Herein, by employing reference electrode in batteries, we revisit the associated physical interpretation of EIS at different frequencies. Combining different battery configurations, temperature‐dependent experiments, and elaborated distribution of relaxation time analysis, we find that the ion transport in porous electrode channels and pseudo‐capacitance behavior dominate the high‐frequency and mid‐frequency impedance arcs, respectively. This work offers a perspective for the physical interpretation of EIS and also sheds light on the understanding of EIS characteristics in other advanced energy storage systems.