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Modeling and simulation play a key role in analyzing the complex electrochemical behavior of lithium-ion batteries. We present the development of a thermodynamic and kinetic modeling framework for intercalation electrochemistry within the open-source software Cantera. Instead of using equilibrium potentials and single-step Butler-Volmer kinetics, Cantera is based on molar thermodynamic data and mass-action kinetics, providing a physically-based and flexible means for complex reaction pathways. Herein, we introduce a new thermodynamic class for intercalation materials into the open-source software. We discuss the derivation of molar thermodynamic data from experimental half-cell potentials, and provide practical guidelines. We then demonstrate the new class using a single-particle model of a lithium cobalt oxide/graphite lithium-ion cell, implemented in MATLAB. With the present extensions, Cantera provides a platform for the lithium-ion battery modeling community both for consistent thermodynamic and kinetic models and for exchanging the required thermodynamic and kinetic parameters. We provide the full MATLAB code and parameter files as supplementary material to this article.

The measurement of the active material volume fraction in composite electrodes of lithium-ion battery cells is difficult due to the small (sub-micrometer) and irregular structure and multi-component composition of the electrodes, particularly in the case of blend electrodes. State-of-the-art experimental methods such as focused ion beam/scanning electron microscopy (FIB/SEM) and subsequent image analysis require expensive equipment and significant expertise. We present here a simple method for identifying active material volume fractions in single-material and blend electrodes, based on the comparison of experimental equilibrium cell voltage curve (open-circuit voltage as function of charge throughput) with active material half-cell potential curves (half-cell potential as function of lithium stoichiometry). The method requires only (i) low-current cycling data of full cells, (ii) cell opening for measurement of electrode thickness and active electrode area, and (iii) literature half-cell potentials of the active materials. Mathematical optimization is used to identify volume fractions and lithium stoichiometry ranges in which the active materials are cycled. The method is particularly useful for model parameterization of either physicochemical (e.g., pseudo-two-dimensional) models or equivalent circuit models, as it yields a self-consistent set of stoichiometric and structural parameters. The method is demonstrated using a commercial LCO–NCA/graphite pouch cell with blend cathode, but can also be applied to other blends (e.g., graphite–silicon anode).

Instabilities of the interface between two thin liquid films under DC electroosmotic flow are investigated using linear stability analysis followed by an asymptotic analysis in the long-wave limit. The two-liquid system is bounded by two rigid plates which act as substrates. The Boltzmann charge distribution is considered for the two electrolyte solutions and gives rise to a potential distribution in these liquids. The effect of van der Waals interactions in these thin films is incorporated in the momentum equations through the disjoining pressure. Marginal stability and growth rate curves are plotted in order to identify the thresholds for the control parameters when instabilities set in. If the upper liquid is a dielectric, the applied electric field can have stabilizing or destabilizing effects depending on the viscosity ratio due to the competition between viscous and electric forces. For viscosity ratio equal to unity, the stability of the system gets disconnected from the electric parameters like interface zeta potential and electric double-layer thickness. As expected, disjoining pressure has a destabilizing effect, and capillary forces have stabilizing effect. The overall stability trend depends on the complex contest between all the above-mentioned parameters. The present study can be used to tune these parameters according to the stability requirement.

The instability of ultra-thin films of an electrolyte bordering a dielectric gas in an external tangential electric field is scrutinized. The solid wall is assumed to be either a conducting or charged dielectric surface. The problem has a steady one-dimensional solution. The theoretical results for a plug-like velocity profile are successfully compared with available experimental data. The linear stability of the steady-state flow is investigated analytically and numerically. Asymptotic long-wave expansion has a triple-zero singularity for a dielectric wall and a quadruple-zero singularity for a conducting wall, and four (for a conducting wall) or three (for a charged dielectric wall) different eigenfunctions. For infinitely small wave numbers, these eigenfunctions have a clear physical meaning: perturbations of the film thickness, of the surface charge, of the bulk conductivity, and of the bulk charge. The numerical analysis provides an important result: the appearance of a strong short-wave instability. At increasing Debye numbers, the short-wave instability region becomes isolated and eventually disappears. For infinitely large Weber numbers, the long-wave instability disappears, while the short-wave instability persists. The linear stability analysis is complemented by a nonlinear direct numerical simulation. The perturbations evolve into coherent structures; for a relatively small external electric field, these are large-amplitude surface solitary pulses, while for a sufficiently strong electric field, these are short-wave inner coherent structures, which do not disturb the surface.

One of the bottlenecks hindering the usage of polymer electrolyte membrane fuel cell technology in automotive applications is the highly load-sensitive degradation of the cell components. The cell failure cases reported in the literature show localized cell component degradation, mainly caused by flow-field dependent non-uniform distribution of reactants. The existing methodologies for diagnostics of localized cell failure are either invasive or require sophisticated and expensive apparatus. In this study, with the help of a multiscale simulation framework, a single polymer electrolyte membrane fuel cell (PEMFC) model is exposed to a standardized drive cycle provided by a system model of a fuel cell car. A 2D multiphysics model of the PEMFC is used to investigate catalyst degradation due to spatio-temporal variations in the fuel cell state variables under the highly transient load cycles. A three-step (extraction, oxidation, and dissolution) model of platinum loss in the cathode catalyst layer is used to investigate the cell performance degradation due to the consequent reduction in the electro-chemical active surface area (ECSA). By using a time-upscaling methodology, we present a comparative prediction of cell end-of-life (EOL) under different driving behavior of New European Driving Cycle (NEDC) and Worldwide Harmonized Light Vehicles Test Cycle (WLTC).