Second-Harmonic Nonlinear Electrochemical Impedance Spectroscopy: Part II. Model-Based Analysis of Lithium-Ion Battery Experiments

Quantitative analysis of electrochemical impedance spectroscopy (EIS) and 2nd-harmonic nonlinear EIS (2nd-NLEIS) data from commercial Li-ion batteries is performed using the porous electrode half-cell models developed in Part I. Because EIS and 2nd-NLEIS signals have opposite parity, the full-cell EIS model relies on the sum of cathode and anode half-cells whereas the full-cell 2nd-NLEIS model requires subtraction of the anode half-cell from the cathode. The full-cell EIS model produces a low error fit to EIS measurements, but importing EIS best-fit parameters into the 2nd-NLEIS model fails to ensure robust model-data convergence. In contrast, simultaneously fitting opposite parity EIS and 2nd-NLEIS models to the corresponding magnitude-normalized experimental data provides a lower total error fit, more internally self-consistent parameters, and better assignment of parameters to individual electrodes than EIS analysis alone. Our results quantify the extent that mild aging of cells (<1% capacity loss) results in substantial increases in cathode charge transfer resistance, and for the first time, a breakdown in cathode charge transfer symmetry at 30% and lower state-of-charge (SoC). New avenues for model-based analysis are discussed for full-cell diagnostic and we identify several open questions.