Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane
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- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States); Joint Center for Energy Storage Research (JCESR), Lemont, IL (United States)
© 2019 American Chemical Society. Molecular clustering and associated dynamic processes of lithium polysulfide species were unraveled using classical molecular dynamics and ab initio metadynamics calculations. The spectroscopic signatures of polysulfide clusters were analyzed using a multimodal analysis including experimental and computational nuclear magnetic resonance (NMR) and X-ray absorption spectroscopies. Lithium polysulfide solutes (Li2S4, Li2S6, and Li2S8) and their mixtures in a 1,3-dioxolane and 1,2-dimethoxyethane (DOL/DME) solvent undergo aggregation driven by intramolecular lithium-sulfur (Li-S) interactions, leading to distributions of cluster sizes, which could critically influence the functioning of lithium-sulfur batteries. Representative polysulfide clusters with systematic increases in molecular size were extracted from the classical molecular dynamics trajectories for subsequent structural and spectroscopic property calculations using density functional theory analysis. Structural analysis of these clusters reveals progressively decreasing solvent involvement in Li+ coordination varying from Li2S4 to Li2S8, with more pronounced variation and changes in DME compared with those in DOL. These observations are reflected in the analysis of the experimental and theoretical 7Li and 17O NMR chemical shifts and pulsed field gradient-NMR diffusion measurements. A comparison of experimental and theoretical S K-edge X-ray absorption near edge spectra shows that relatively large lithium sulfide chain clusters are likely to occur in the DOL/DME-solvated lithium sulfide systems. Ab initio metadynamics simulations and NMR analysis indicate that Li+ solvated by only the solvent can occur through Li+ dissociation from sulfide chains. However, the occurrence of "sulfide-free" Li+ is a minor mechanism compared with the dynamic aggregation and shuttling processes of polysulfide solvates in DOL/DME-based electrolytes of Li-S batteries. Overall, atomistic insights gained about clustering and lithium exchange dynamics will be critical for the predictive understanding of the polysulfide shuttling and nucleation process that dictates the Li-S battery performance.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Laboratory Directed Research and Development (LDRD) Program; National Research Council Canada (NRC)
- Grant/Contract Number:
- AC02-06CH11357; AC02-05CH11231; AC05-76RL01830; AC02-05CH1123
- OSTI ID:
- 1529348
- Alternate ID(s):
- OSTI ID: 1530600; OSTI ID: 1769304
- Report Number(s):
- PNNL-SA-141178
- Journal Information:
- Chemistry of Materials, Vol. 31, Issue 7; ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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