On the Structure of Sulfur/1,3‐Diisopropenylbenzene Co‐Polymer Cathodes for Li‐S Batteries: Insights from Density‐Functional Theory Calculations

Sulfur co‐polymers have recently drawn considerable attention as alternative cathode materials for lithium‐sulfur batteries, thanks to their flexible atomic structure and the ability to provide high reversible capacity. Here, we report on the atomic structure of sulfur/1,3‐diisopropenylbenzene co‐polymers (poly(S‐co‐DIB)) based on the insights obtained from density‐functional theory calculations. The focus is set on studying the local structural properties, namely the favorable sulfur chain length (S( n ) with [Formula: see text] ) connecting two DIBs. In order to investigate the effects of the organic groups and sulfur chains separately, we perform series of atomic structure optimizations. We start from simple organic groups connected via sulfur chains and gradually change the structure of the organic groups until we reach a structure in which two DIB molecules are attached via sulfur chains. Additionally, to increase the structural sampling, we perform temperature‐assisted minimum‐energy structure search on slightly simpler model systems. We find that in DIB‐S( n )‐DIB co‐polymers, shorter sulfur chains with [Formula: see text] are preferred, where the stabilization is mostly brought about by the sulfur chains rather than the organic groups. The presented results, corresponding to the fully charged state of the cathode in the thermodynamic limit, have direct applications in the field of lithium‐sulfur batteries with sulfur‐polymer cathodes.