Mechano-Electro-Chemical Impedance Spectroscopy (MeIS): Concept, Theory and Experiment

Electrochemical impedance spectroscopy (EIS) is a widely used non-invasive method for characterizing and diagnosing lithium-ion batteries (LIBs) 1 . The key to utilizing EIS lies in interpreting the measured impedance spectrum. This involves fitting the experimental data to an impedance model to understand the internal states of the battery. However, due to the multiscale and multiphysical nature of LIBs, impedance models can be complex and have many parameters. As a result, there is a high risk of over-fitting the experimental data, making the interpretation of the EIS data challenging 2 . In addition to electrical signals, the mechanical responses of a LIB, such as pressure and thickness change during charge/discharge, provides valuable information for characterization and diagnosis 3-5 . Most existing analyses of mechanical signals focus on the time domain. Recently, von Kessel et al 6 introduced Mechanical Impedance Spectroscopy (MIS) as a frequency-analyzing tool for characterizing LIBs. The MIS spectrum (the displacement response subject to a cyclic pressure trigger) turned out to vary with the state of the batteries, demonstrating the great potential of using mechanical responses in the frequency domain to characterize and diagnosis the LIBs. Nevertheless, measuring displacement for LIBs in real-world applications is challenging, as it requires a customized testing machine to measure the micrometer-level displacement while exerting a sinusoidal pressure input. This requirement for customized testing equipment limits the application scope of the MIS method. A free LIB cell cyclic changes its dimensions during charge/discharge. Under confinements where dimension change constricted, cyclic pressure change will be generated, which could be used for frequency analysis. This observation led us to propose a new method called mechano-electro-chemical impedance spectroscopy (MeIS). An MeIS spectrum is defined as the ratio of pressure perturbation to the input current, denoted as . Measurements can be obtained by perturbating the battery with sinusoidal current and recording the resulting pressure or displacement response. The basic transfer function for MeIS is derived from the electro-chemo-mechanical coupling of the porous electrode. The MeIS consists of two parts, the MIS term and an electrochemical term resulting from the insertion/extraction deformation of the electroactive particles. The great advantage of MeIS is that it requires only a pressure or displacement sensor and a charger capable of providing sinusoidal current, making it potentially applicable in in-field scenarios such as management of EV batteries or real-time monitoring of a battery-based energy storage facility. Sensitivity analysis reveals that MeIS is highly sensitive to changes in the structure of porous electrodes, thus providing valuable insights into the internal structural integrity and degradation of LIBs. In addition, the experimental design and demonstrational results are also provided. We believe that MeIS could serve as a convenient and useful complement to EIS, enhancing the non-invasive diagnostic toolbox for LIBs. Reference: K. Mc Carthy, H. Gullapalli, K. M. Ryan, and T. Kennedy, Journal of The Electrochemical Society, 168 (8), (2021). F. Ciucci, Current Opinion in Electrochemistry, 13 132-139 (2019). J. Zhu, T. Wierzbicki, and W. Li, Journal of Power Sources, 378 153-168 (2018). B. Rieger, S. Schlueter, S. V. Erhard, J. Schmalz, G. Reinhart, and A. Jossen, Journal of Energy Storage, 6 213-221 (2016). Z. J. Schiffer, J. Cannarella, and C. B. Arnold, Journal of The Electrochemical Society, 163 (3), A427-A433 (2015). O. von Kessel, T. Deich, S. Hahn, F. Brauchle, D. Vrankovic, T. Soczka-Guth, and K. P. Birke, Journal of Power Sources, 508 (2021). Figure 1