Sulfur cathodes represent a promising solution to meet the growing demand for cost-effective, sustainable, and high-energy-density energy storage systems utilizing abundant elements. However, their commercialization re- mains challenging due to the complex metal‐sulfur reactions, which often involve solid-liquid phase transitions, as well as the dissolution and migration of polysulfides. Addressing these challenges requires a deeper under- standing and systematic optimization of these processes. In this study, we present a three-step zero-dimensional (0D) electrochemical model based on Nernst formulations and Butler–Volmer kinetics designed to simulate the performance of sulfur cathodes. Focusing on lithium‐sulfur batteries (LSBs) as a case study, the model in- corporates key phenomena, including the multiple electrochemical reactions involved in the conversion of sulfur to lithium sulfide, precipitation of S2− , and the shuttle effect. To validate the model, we utilize sulfur cathodes composed of Li2S supported on Ketjen Black (KB) and incorporating cobalt nanoparticles (Li2S-Co@KB). The developed model is employed to simulate discharge curve using a hybrid optimization approach combining Bayesian and the Nelder-Mead algorithms. The model’s predictive capability is evaluated by assessing its ability to replicate the experimental voltage profiles of LSBs. Additionally, the error between the simulated and experimental voltage curves is analyzed to demonstrate the model’s accuracy and reliability.

Keywords