Charge Transfer Parameters of Nix_{x}Mny_{y}Co1−x−y_{1-x-y} Cathodes Evaluated by a Transmission Line Modeling Approach

The performance of lithium‐ion batteries can be analyzed and improved by appropriate electrochemical models. A challenging yet crucial part is the parameterization of these models. Until now, the literature has incompletely investigated and cited the charge transfer process parameters describing the lithium transfer between the active material particles in the electrode and the liquid electrolyte. Herein, a novel approach is presented for obtaining these charge transfer parameters. The well‐established experimental methods of electrochemical impedance spectroscopy and focused ion beam tomography are applied. By introducing both experimental results into a transmission line model, a reliable determination of the charge transfer parameters j$_{0}$, k, and r$_{CT}$ can be achieved. The new approach is validated by comparing the results of four cathodes, all containing the state‐of‐the‐art active material Ni$_{x}$Mn$_{y}$Co$_{1-x-y}$ (NMC), but with different microstructures and/or stoichiometries

Capacity Fade in Lithium-Ion Batteries and Cyclic Aging over Various State-of-Charge Ranges

In order to develop long-lifespan batteries, it is of utmost importance to identify the relevant aging mechanisms and their relation to operating conditions. The capacity loss in a lithium-ion battery originates from (i) a loss of active electrode material and (ii) a loss of active lithium. The focus of this work is the capacity loss caused by lithium loss, which is irreversibly bound to the solid electrolyte interface (SEI) on the graphite surface. During operation, the particle surface suffers from dilation, which causes the SEI to break and then be rebuilt, continuously. The surface dilation is expected to correspond with the well-known graphite staging mechanism. Therefore, a high-power 2.6 Ah graphite/LiNiCoAlO2 cell (Sony US18650VTC5) is cycled at different, well-defined state-of-charge (SOC) ranges, covering the different graphite stages. An open circuit voltage model is applied to quantify the loss mechanisms (i) and (ii). The results show that the lithium loss is the dominant cause of capacity fade under the applied conditions. They experimentally prove the important influence of the graphite stages on the lifetime of a battery. Cycling the cell at SOCs slightly above graphite Stage II results in a high active lithium loss and hence in a high capacity fade

A multi scale multi domain model for large format lithium-ion batteries

A multi scale multi domain (MSMD) model for large format lithium-ion battery (LIB) cells is presented. In our approach the homogenization is performed on two scales (i) from the particulate electrodes to homogenized electrode materials using an extended Newman model and (ii) from individual cell layer materials to a homogenized battery material with anisotropic electrical and thermal transport properties. Both intertwined homogenizations are necessary for considering electrochemical-thermal details related to microstructural and material features of electrode and electrolyte layers at affordable computational costs. Simulation results validate the MSMD model compared to the homogenized Newman model for isothermal cases. The strength of the MSMD model is demonstrated for non-isothermal conditions, namely for a 120 Ah cell discharged with four different cooling concepts: (i) without cooling (ii) with a base plate cooling (iii) with a tab cooling and (iv) with a side cooling. As one result, temperature gradients cause a local peak discharge up to 2.8 C for a global 2 C discharge rate

Understanding Deviations between Spatially Resolved and Homogenized Cathode Models of Lithium‐Ion Batteries

Porous electrode models are essential for inexpensively predicting the performance and lifetime of lithium‐ion batteries. Physics‐based models range from microscopic 3D models, which spatially resolve the microstructural characteristics of all phases in porous electrodes, to reduced and computationally effective models, which do not resolve the microstructure. The homogenized Newman model, also known as the pseudo‐2D (P2D) model, is well established and widely used. However, the necessary simplification shows its weaknesses, especially for high charge and discharge rates, and these lead to significant differences in comparison with the microscopic 3D model. Herein, the validity of the homogenized Newman model is investigated with respect to variations of the microstructural characteristics of a porous cathode. The effects of 1) a homogenized conductive additive; 2) non‐spherical particle geometries; and 3) overlapping particles on charge/discharge curves are analyzed. The result is a better understanding of the validity limits of P2D models. These new insights about the individual influences of the simplifications will be used to improve the homogenized model. The simulation of complex cathode structures, where several homogenization assumptions are violated, shows that the improved homogenized model reaches a very high accuracy, and, thus, overcomes the existing limitations of the P2D model approach

Optimization of Material Contrast for Efficient FIB‐SEM Tomography of Solid Oxide Fuel Cells

Focused ion beam (FIB) – scanning electron microscopy (SEM) serial sectioning tomography has become an important tool for three‐dimensional microstructure reconstruction of solid oxide fuel cells (SOFC) to obtain an understanding of fabrication‐related effects and SOFC performance. By sequential FIB milling and SEM imaging a stack of cross‐section images across all functional SOFC layers was generated covering a large volume of 3.5·10$^{4}$ μm$^{3}$. One crucial step is image segmentation where regions with different image intensities are assigned to different material phases within the SOFC. To analyze all relevant SOFC materials, it was up to now mandatory to acquire several images by scanning the same region with different imaging parameters because sufficient material contrast could otherwise not be achieved. In this work we obtained high‐contast SEM images from a single scan to reconstract all functional SOFC layers consisting of a Ni/Y$_{2}$O$_{3}$‐doped ZrO$_{2}$ (YDZ) cermet anode, YDZ electrolyte and (La,Sr)MnO$_{3}$/YDZ cathode. This was possible by using different, simultaneous read‐out detectors installed in a state‐of‐the‐art scanning electron microscope. In addition, we used a deterministic approach for the optimization of imaging parameters by employing Monte Carlo simulations rather than trial‐and‐error tests. We also studied the effect of detection geometry, detecting angle range and detector type