No abstract

The electrification of the powertrain requires enhanced performance of lithium-ion batteries, mainly in terms of energy and power density. They can be improved by optimising the positive electrode, i.e., by changing their size, composition or morphology. Thick electrodes increase the gravimetric energy density but generally have an inefficient performance. This work presents a 2D modelling approach for better understanding the design parameters of a thick LiFePO4 electrode based on the P2D model and discusses it with common literature values. With a superior macrostructure providing a vertical transport channel for lithium ions, a simple approach could be developed to find the best electrode structure in terms of macro- and microstructure for currents up to 4C. The thicker the electrode, the more important are the direct and valid transport paths within the entire porous electrode structure. On a smaller scale, particle size, binder content, porosity and tortuosity were identified as very impactful parameters, and they can all be attributed to the microstructure. Both in modelling and electrode optimisation of lithium-ion batteries, knowledge of the real microstructure is essential as the cross-validation of a cellular and lamellar freeze-casted electrode has shown. A procedure was presented that uses the parametric study when few model parameters are known.

Zinc-air batteries could be a key technology for higher energy densities of electrochemical energy storage systems. Many questions remain unanswered, however, and new methods for analyses and quantifications are needed. In this study, the distribution of relaxation times (DRT) based on ridge regression was applied to the impedance data of primary zinc-air batteries in a temperature range of 253 K and 313 K and at different State-of-Charges for the first time. Furthermore, the problem of the regularization parameter on real impedance spectroscopic measurements was addressed and a method was presented using the reconstruction of impedance data from the DRT as a quality criterion. The DRT was able to identify a so far undiscussed process and thus explain why some equivalent circuit models may fail.

The performance of batteries and the associated operating areas depend, among other things, on the 3D microstructures of the electrode materials, and thus fundamental research is required in the field of electrode design. A multiscale microstructure‐resolved 3D model is developed that investigates two different LiFePO4 freeze‐casted electrode structures, that is, cellular and lamellar. The microstructure is simulated directly from the X‐ray computed tomography data and the nanostructure is combined with the pseudo‐2D simulation approach, where the morphological parameters and the distribution of the binder, carbon, and LiFePO4 are obtained from ex situ focused ion beam scanning electron microscopy measurements. The discharge performance shows that the lamellar structure exhibits a lower ohmic overvoltage and achieves a higher gravimetric capacity compared to the cellular structure, even though both electrode materials have the same porosity and amount of active material. The simulation reveals that the performance is not only directly influenced by the lithium‐ion transport through the porous structure but also by the current distribution through the active material. Based on these insights, lamellar electrode structures should be considered for next‐generation battery electrodes. The modeling approach can assist in electrode fabrication by identifying defects or suggesting better structural parameters.