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 n ¼ 1 � � � 8) 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 n � 4 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.

Optimization of lithium-sulfur batteries highly depends on exploring and characterizing new cathode materials. Sulfur/carbon copolymers have recently attracted much attention as an alternative class of cathodes to replace crystalline sulfur. In particular, poly(sulfur-n-1,3-diisopropenylbenzene) (S/DIB) has been under considerable experimental and theoretical investigations, promising a good performance in mitigating the so-called shuttle effect. Here, combining ab initio Raman spectroscopy simulations with experimental measurements, we show that S/DIB copolymers containing short and long sulfur chains are distinguishable based on their Raman activity in 400-500 1/cm. This frequency range corresponds to S--S stretching vibrations and is only observed in the Raman spectra of those copolymers with longer sulfur chains. The results reported in this study have direct applications in identification and characterization of general sulfur/carbon copolymers with different sulfur contents.

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