High-energy lithium/sulfur (Li/S) batteries still suffer from unsatisfactory cycle life and poor rate capability caused by the polysulfides shuttle and insulating nature of S cathodes. Here, we report our findings in the controlled synthesis of selenium (Se)-containing S-rich co-polymers of various compositions as novel cathode materials through a facile inverse vulcanization of S with selenium disulfide (SeS2) and 1,3-diisopropenylbenzene (DIB) as co-monomers. Nuclear magnetic resonance and X-ray photoelectron spectroscopy results show that divinyl functional groups of DIB were chemically cross-linked with S/SeS2 chain radicals through a ring-opening polymerization. The newly formed bonds of C-S, C-Se, and S-Se in novel S-SeS2-DIB co-polymers effectively alleviate the shuttle effects of polysulfides/polyselenides. Furthermore, various electrochemical techniques confirm the positive roles of Se-containing co-polymers in enhancing the electrode reaction kinetics and the formation of stable solid electrolyte interphase layer with low charge-transfer resistance, leading to improved high-rate performances. The as-synthesized co-polymer was then infiltrated into well-interconnected, porous nanocarbon networks (Ketjenblack EC600JD, KB600) to provide effective paths for the fast electron transport. Due to the synergistic combination of chemical and physical confinement of the reaction intermediates during cycling, good reversibility for 500 cycles with a low decay rate of 0.0549% per cycle was achieved at 1000 mA g-1. These encouraging results suggest that the combination of chemical incorporation of SeS2 into S-rich co-polymer and the physical confinement of carbon networks is a promising strategy for advancing Li/S batteries and their viability for practical applications.
Keywords: inverse vulcanization; lithium batteries; selenium sulfides; sulfur cathodes; sulfur-rich co-polymers.