Lithium-sulfur batteries show remarkable potential for energy storage applications due to their high-specific capacity and the low cost of active materials, especially sulfur. However, whereas there is a consensus about the use of lithium metal as the negative electrode, there is not a clear and widely accepted architectural design for the positive electrode of sulfur batteries. The difficulties arise when trying to find a balance between high-surface-area architectures and practical utilization of the sulfur content. Intensive understanding of the interfacial mechanisms becomes then crucial to design optimized carbon-hosted sulfur architectures with enhanced electrochemical performance. In this work, we use density functional theory (DFT)-based first principles calculations to describe and characterize the growing mechanisms of Li2S active material on graphene, taken as an example of a nonencapsulated carbon host for the positive electrode of Li-S batteries. We first unravel the two growing mechanisms of Li2S supported nanostructures, which explain recent experimental findings on real-time monitoring of interfacial deposition of lithium sulfides during discharge, obtained by means of in situ atomic force microscopy. Then, using a combination of mathematical tools and DFT calculations, we obtain the first cycle voltage plot, explaining the three different regions observed that ultimately lead to the formation of high-order polysulfides upon charge. Finally, we show how the different Li2S supported nanostructures can be characterized in X-ray photoelectron spectroscopy measurements. Altogether, this work provides useful insights for the rational design of new carbon-hosted sulfur architectures with optimized characteristics for the positive electrode of lithium-sulfur batteries.
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