Lithium-sulfur batteries are amongst the most appealing choices for the next generation large-scale energy storage applications. However, these batteries still suffer several formidable performance degradation issues that impede its commercialization. The lithium negative electrode yields high anodic capacity, but it causes dendrite formation and raises safety concerns. Furthermore, the high reactivity of lithium is accountable for electrolyte decomposition. To investigate these issues and possible countermeasures, we used ReaxFF reactive molecular dynamics simulations to elucidate anode-electrolyte interfacial chemistry and utilized an ex-situ anode surface treatment with Teflon coating. In this study, we employed Li/SWCNT (single-wall carbon nanotube) composite anode instead of lithium metal and tetra(ethylene glycol) dimethyl ether (TEGDME) as electrolyte. We find that at lithium rich environment at the anode-electrolyte interface, electrolyte dissociates and generates ethylene gas as a major reaction product, while utilization of Teflon layer suppresses the lithium reactivity and reduces electrolyte decomposition. Lithium discharge from the negative electrode is an exothermic event that creates local hot spots at the interfacial region and expedites electrolyte dissociation reaction kinetics. Usage of Teflon dampens initial heat flow and effectively reduces lithium reactivity with the electrolyte. (C) 2014 The Electrochemical Society. All rights reserved.