Confined Lithium–Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity
Oviedo, M. Belén
von Wald Cresce, Arthur
Itkis, Mikhail E.
Haddon, Robert C.
Wong, Bryan M.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Chemical Science Program
Nanostructured Functional Materials (NFM) laboratory
Physical Science and Engineering (PSE) Division
Online Publication Date2018-09-24
Print Publication Date2018-10-23
Embargo End Date2019-09-24
Permanent link to this recordhttp://hdl.handle.net/10754/630570
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AbstractWe demonstrate an unusual electrochemical reaction of sulfur with lithium upon encapsulation in narrow-diameter (subnanometer) single-walled carbon nanotubes (SWNTs). Our study provides mechanistic insight on the synergistic effects of sulfur confinement and Li+ ion solvation properties that culminate in a new mechanism of these sub-nanoscale-enabled reactions (which cannot be solely attributed to the lithiation-delithiation of conventional sulfur). Two types of SWNTs with distinct diameters, produced by electric arc (EA-SWNTs, average diameter 1.55 nm) or high-pressure carbon monoxide (HiPco-SWNTs, average diameter 1.0 nm), are investigated with two comparable electrolyte systems based on tetraethylene glycol dimethyl ether (TEGDME) and 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5). Electrochemical analyses indicate that a conventional solution-phase Li-S reaction occurs in EA-SWNTs, which can be attributed to the smaller solvated [Li(TEGDME)]+ and [Li(15-crown-5)]+ ions within the EA-SWNT diameter. In stark contrast, the Li-S confined in narrower diameter HiPco-SWNTs exhibits unusual electrochemical behavior that can be attributed to a solid-state reaction enabled by the smaller HiPco-SWNT diameter compared to the size of solvated Li+ ions. Our results of the electrochemical analyses are corroborated and supported with various spectroscopic analyses including operando Raman, X-ray photoelectron spectroscopy, and first-principles calculations from density functional theory. Taken together, our findings demonstrate that the controlled solid-state lithiation-delithiation of sulfur and an enhanced electrochemical reactivity can be achieved by sub-nanoscale encapsulation and one-dimensional confinement in narrow-diameter SWNTs.
CitationFu C, Oviedo MB, Zhu Y, von Wald Cresce A, Xu K, et al. (2018) Confined Lithium–Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity. ACS Nano 12: 9775–9784. Available: http://dx.doi.org/10.1021/acsnano.7b08778.
SponsorsXPS work was performed at the UC Irvine Materials Research Institute (IMRI) using instrumentation funded in part by the National Science Foundation Major Research Instrumentation Program under grant no. CHE-1338173. M.B.O. and B.M.W. acknowledge the National Science Foundation for the use of supercomputing resources through the Extreme Science and Engineering Discovery Environment (XSEDE), project no. TG-ENG160024. Electron microscopy work (EELS) was conducted as part of a user project at ORNL’s Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. B.M.W. and J.G. acknowledge the National Science Foundation for financial support under grant no. CBET-1604908.
PublisherAmerican Chemical Society (ACS)