Electrochemical impedance spectroscopy (EIS) is a powerful and non-destructive characterization technique widely used in the electrochemical research field. It can measure many macroscopic properties such as internal resistance, capacitance, and diffusivity by fitting the obtained impedance with equivalent circuits. Each of the acquired quantities reflects an electrochemical mechanism, e.g, charge-transfer reaction, double layer formation, and mass transport, taking place in the electrode. However, the obtained quantity is a total value for the whole electrode. The underlying connections between the macroscopic properties, intrinsic material parameters, and electrode microstructures are not well understood. This dissertation focuses on building a modeling framework to simulate EIS processes with given electrode microstructures and intrinsic material parameters. With this simulation tool, we provide a digital bridge between battery electrode material properties, electrode microstructures, and their corresponding EIS impedance. Capacitance of an electrochemical device originates from double layer formation in the electrolyte. However, there is a huge spatial discrepancy between the dimensions of double layer and electrode particles (or interparticle space). Thus, smoothed boundary method and adaptive mesh refinement are used to handle the scale discrepancy and the complex geometries of electrode particles in solving the Nernst-Planck-Poisson equations in simulating the double layer formation under voltage loading.The obtained double-layer capacitance is incorporated into multiphysics electrochemical simulations. Cathode electrode made of Nickel-Manganese-Cobalt (NMC111) oxide, is examined with this simulation tool. As a solid solution material, lithium transport in the NMC111 electrode particles is described by Fick's law. EIS curves for various conditions, including different states of charge, electrolyte salt concentration, electrode microstructures, are extracted from the simulations and analyzed. The simulations properly reflect the relationships between particle exchange current density, reactive surface area, and the total resistance of the electrode.Anodes made of graphite, a phase-transforming material upon lithiation/delithiation, are also examined using the simulation tool. The Cahn-Hilliard equation is employed to model the phase transformation processes in the particles. EIS simulations are conducted on single-phase and multi-phase graphite. For single-phase or core-shell phase-distributed graphite particles, the simulated EIS curves exhibit a typical semicircle with a Warburg part. Interestingly, if phase boundaries intersect particle surfaces, a low frequency inductive loop appears on the EIS curve. Lastly, the simulation tool is applied to simulate EIS processes of a full-cell battery of both cathode and anode microstructures. On each electrode, the total current is comprised of capacitance and reaction currents. It is observed that, depending on the loading frequency, the ratio of capacitance-to-reaction current on the two electrodes can be significantly different. The simulation tool allows us to examine the details of electrochemical processes during EIS measurements.
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