Iron-nitrogen functionalized graphene has emerged as a promising cathode host for rechargeable lithium-sulfur batteries (RLSBs) due to its affordability and enhanced battery performance. To optimize its catalytical efficiency, we propose a novel approach involving coordination engineering. Our investigation spans a plethora of catalysts with varied coordination environments, focusing on elements B, C, N and O. We revealed that Fe-C4 and Fe-B2C2-h are particularly effective for promoting Li2S oxidation, whereas Fe-N4 excels in catalyzing the sulfur reduction reaction (SRR). Importantly, our study identified specific descriptors - namely, the Integrated Crystal Orbital Hamilton Population (ICOHP) and the bond length between Fe and S in Li2S adsorbed state - as the most effective predictive descriptors for Li2S oxidation barriers. Meanwhile, Li2S adsorption energy emerges as a reliable descriptor for assessing the SRR barrier. These identified descriptors are expected to be instrumental in rapidly identifying promising cathode hosts across various metal-centered systems with diverse coordination environments. Our findings not only offer valuable insights into the role of coordination environment, but also present an effective path for rapidly identifying high performance catalysts for RLSBs, enabling the acceleration of advanced RLSBs development.
Keywords: Coordination environment; Descriptors; First-principles calculations; Graphene; Lithium-sulfur batteries.
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