XCT Images-Based Modeling for Elucidating Electrochemical Inert Phase-Dependent Multiscale Electrode Kinetic Behaviors

Abstract

The electrochemically inert phase (EIP) within the electrode is formed by the combination of carbon black and binder, characterized by a highly heterogeneous spatial distribution and structural morphology. This heterogeneity impairs electrode performance under varying discharge rates and temperatures. In this study, X-ray computed tomography is employed to image the original electrode. The resulting grayscale images are digitally processed to reveal the two-dimensional (2D) and three-dimensional (3D) features of the EIP morphology, thereby providing a design window to understand the influence of EIP morphology. The physical structure characterization indicates that, compared to bulk-like EIP (B-EIP), film-like EIP (F-EIP) tends to cover the active surface of the active material (AM), exacerbating the heterogeneity of the lithiation reactions within the electrode. The reduction in the AM active surface area correlates the state of lithiation (SOL) of particles with their active specific surface area (α_a). At low temperatures, the temperature sensitivity of electrodes intensifies the risk of α_a loss, promoting heterogeneous reaction transfer between particles. The Biot number (Bi) is used to evaluate the competing mechanisms between interfacial reactions and bulk diffusion within particles. In electrodes with a high EIP content, the reaction rate at the particle/electrolyte interface is accelerated, causing particle performance to be dominated by interfacial reactions. Finally, the electrochemistry and heat generation from the particle-level to the electrode-level in thicker electrodes are examined. It demonstrates that ion diffusion in the pore controls interfacial reactions and heat transport behavior. Aggregated high-flux reactions and localized hot spots exacerbate the heterogeneous degradation and side reactions within the electrode.