Multimodal Operando Analysis of Lithium Sulfur Multilayer Pouch Cells: An In‐Depth Investigation on Cell Component Design and Performance

Abstract This study presents an innovative operando analysis of lithium‐sulfur (Li/S) multilayer pouch cells, employing a combination of lab‐source and synchrotron x‐ray imaging to investigate sulfur crystallite dissolution and lithium dendrite formation. By integrating advanced X‐ray imaging, impedance spectroscopy, and simultaneous monitoring of temperature and pressure, the research uncovers critical insights into the behavior of active and inactive cell components. The analysis reveals significant degradation increments, primarily driven by side product accumulation and the deterioration of lithium microstructures, which contribute to performance loss over cycling. Additionally, temperature distribution analysis shows a strong correlation between joule heating, polarization resistance, and the observed endothermic processes during crystallization. These findings provide a comprehensive understanding of the mechanistic processes within industrially relevant pouch cells, highlighting opportunities for optimizing Li/S cell designs and advancing high‐energy‐density battery systems for commercial applications.