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This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics aging model of a 500 mAh high-energy lithium-ion pouch cell with graphite negative electrode and lithium nickel manganese cobalt oxide (NMC) positive electrode. This model includes electrochemical reactions for solid electrolyte interphase (SEI) formation at the graphite negative electrode, lithium plating, and SEI formation on plated lithium. The thermodynamics of the aging reactions are modeled depending on temperature and ion concentration and the reactions kinetics are described with an Arrhenius-type rate law. Good agreement of model predictions with galvanostatic charge/discharge measurements and electrochemical impedance spectroscopy is observed over a wide range of operating conditions. The model allows to quantify capacity loss due to cycling near beginning-of-life as function of operating conditions and the visualization of aging colormaps as function of both temperature and C-rate (0.05 to 2 C charge and discharge, −20 °C to 60 °C). The model predictions are also qualitatively verified through voltage relaxation, cell expansion and cell cycling measurements. Based on this full model, six different aging indicators for determination of the limits of fast charging are derived from post-processing simulations of a reduced, pseudo-two-dimensional isothermal model without aging mechanisms. The most successful aging indicator, compared to results from the full model, is based on combined lithium plating and SEI kinetics calculated from battery states available in the reduced model. This methodology is applicable to standard pseudo-two-dimensional models available today both commercially and as open source.
The lifetime of a battery is affected by various aging processes happening at the electrode scale and causing capacity and power fade over time. Two of the most critical mechanisms are the deposition of metallic lithium (plating) and the loss of lithium inventory to the solid electrolyte interphase (SEI). These side reactions compete with reversible lithium intercalation at the graphite anode. Here we present a comprehensive physicochemical pseudo-3D aging model for a lithium-ion battery cell, which includes electrochemical reactions for SEI formation on graphite anode, lithium plating, and SEI formation on plated lithium. The thermodynamics of the aging reactions are modeled depending on temperature and ion concentration, and the reactions kinetics are described with an Arrhenius-type rate law. The model includes also the positive feedback of plating on SEI growth, with the presence of plated lithium leading to a higher SEI formation rate compared to the values obtained in its absence at the same operating conditions. The model is thus able to describe cell aging over a wide range of temperatures and C-rates. In particular, it allows to quantify capacity loss due to cycling (here in % per year) as function of operating conditions. This allows the visualization of aging colormaps as function of both temperature and C-rate and the identification of critical operation conditions, a fundamental step for a comprehensive understanding of batteries performance and behavior. For example, the model predicts that at the harshest conditions (< –5 °C, > 3 C), aging is reduced compared to most critical conditions (around 0–5 °C) because the cell cannot be fully charged.
Fast charging of lithium-ion batteries remains one of the most delicate challenges for the automotive industry, being seriously affected by the formation of lithium metal in the negative electrode. Here we present a physicochemical pseudo-3D model that explicitly includes the plating reaction as side reaction running in parallel to the main intercalation reaction. The thermodynamics of the plating reaction are modeled depending on temperature and ion concentration, which differs from the often-used assumption of a constant plating condition of 0 V anode potential. The reaction kinetics are described with an Arrhenius-type rate law parameterized from an extensive literature research. Re-intercalation of plated lithium was modeled to take place either via reverse plating (solution-mediated) or via an explicit interfacial reaction (surface-mediated). At low temperatures not only the main processes (intercalation and solid-state diffusion) become slow, but also the plating reaction itself becomes slower. Using this model, we are able to predict typical macroscopic experimental observables that are indicative of plating, that is, a voltage plateau during discharge and a voltage drop upon temperature increase. A spatiotemporal analysis of the internal cell states allows a quantitative insight into the competition between intercalation and plating. Finally, we calculate operation maps over a wide range of C-rates and temperatures that allow to assess plating propensity as function of operating condition.
This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics model of a 350 mAh high-power lithium-ion pouch cell with graphite anode and lithium cobalt oxide/lithium nickel cobalt aluminum oxide (LCO/NCA) blend cathode. The model describes transport processes on three different scales: Heat transport on the macroscopic scale (cell), mass and charge transport on the mesoscopic scale (electrode pair), and mass transport on the microscopic scale (active material particles). A generalized description of electrochemistry in blend electrodes is developed, using the open-source software Cantera for calculating species source terms. Very good agreement of model predictions with galvanostatic charge/discharge measurements, electrochemical impedance spectroscopy, and surface temperature measurements is observed over a wide range of operating conditions (0.05C to 10C charge and discharge, 5°C to 35°C). The behavior of internal states (concentrations, potentials, temperatures) is discussed. The blend materials show a complex behavior with both intra-particle and inter-particle non-equilibria during cycling.