Comprehensive Insights into the Porosity of Lithium-Ion Battery Electrodes: A Comparative Study on Positive Electrodes Based on LiNi0.6Mn0.2Co0.2O2 (NMC622)

Porosity is frequently specified as only a value to describe the microstructure of a battery electrode. However, porosity is a key parameter for the battery electrode performance and mechanical properties such as adhesion and structural electrode integrity during charge/discharge cycling. This study illustrates the importance of using more than one method to describe the electrode microstructure of LiNi0.6Mn0.2Co0.2O2 (NMC622)-based positive electrodes. A correlative approach, from simple thickness measurements to tomography and segmentation, allowed deciphering the true porous electrode structure and to comprehend the advantages and inaccuracies of each of the analytical techniques. Herein, positive electrodes were calendered from a porosity of 44–18% to cover a wide range of electrode microstructures in state-of-the-art lithium-ion batteries. Especially highly densified electrodes cannot simply be described by a close packing of active and inactive material components, since a considerable amount of active material particles crack due to the intense calendering process. Therefore, a digital 3D model was created based on tomography data and simulation of the inactive material, which allowed the investigation of the complete pore network. For lithium-ion batteries, the results of the mercury intrusion experiments in combination with gas physisorption/pycnometry experiments provide comprehensive insight into the microstructure of positive electrodes.