DFT Investigation of Soluble and Insoluble Polysulfide Clusters in Metal–Sulfur Systems
POSTER
Abstract
Metal–sulfur batteries are a promising next-generation energy storage technology due to their high gravimetric capacity and energy density. However, a major challenge in these systems is the polysulfide shuttle effect, which leads to the formation and migration of unwanted polysulfide species, ultimately degrading battery performance. To better understand the physical mechanisms underlying the charge–discharge processes in metal–sulfur battery electrodes, Density Functional Theory (DFT) is commonly employed to calculate the adsorption strength of various polysulfides on electrode materials. Accurate structural models of both soluble and insoluble metal polysulfides are essential for these calculations. While the gas-phase structures of lithium polysulfides have been extensively studied, the structural landscape of sodium and potassium polysulfides remains largely unexplored. In this work, we systematically generated hundreds of candidate structures for each Li-, Na-, and K-polysulfide stoichiometry using a swarm intelligence algorithm, i.e. the artificial bee colony (ABC) algorithm, based on Lennard-Jones potentials as implemented in the ABCluster code. These structures were subsequently optimized using DFT methods. Our investigation identified the lowest-energy configurations for each cluster, along with several higher-energy isomers. These results provide insight into the geometric and energetic landscape of metal polysulfides, offering a structural baseline for future studies in electrochemical environments and contributes to the broader effort to develop cost-effective and high-performance metal–sulfur batteries.
*The authors acknowledge the support of the Automotive Research Center (ARC), Cooperative Agreement W56HZV-24-2-0001 U.S. Army DEVCOM GVSC. We also acknowledge computational resources and services provided by the Institute for Cyber-Enabled Research at Michigan State University.
Publication:[1] W. Yao, K. Liao, T. Lai, H. Sul, and A. Manthiram, "Rechargeable Metal–Sulfur Batteries: Key Materials to Mechanisms," Chem. Rev. 124, 4935 (2024).
[2] J. Zhang and M. Dolg, "ABCluster: The Artificial Bee Colony Algorithm for Cluster Global Optimization," Phys. Chem. Chem. Phys. 17, 24173 (2015).
[3] J. P. Perdew, K. Burke, and Y. Wang, "Generalized gradient approximation for the exchange-correlation hole of a many-electron system," Phys. Rev. B 54, 16533 (1996).
[4] B. G. Janesko, T. M. Henderson, and G. E. Scuseria, "Screened hybrid density functionals for solid-state chemistry and physics," Phys. Chem. Chem. Phys. 11, 443 (2008).
