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Confined Lithium–Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity

Journal Article · · ACS Nano
 [1];  [1];  [2];  [3];  [3];  [1];  [1];  [1];  [4];  [5];  [1];  [1]
  1. Univ. of California, Riverside, CA (United States)
  2. Zhejiang University of Technology, Hangzhou (China)
  3. Army Research Lab., Adelphi, MD (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. King Abdullah University of Science and Technology, Thuwal (Saudi Arabia)
+ Show Author Affiliations

Here, we 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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1831714
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 10 Vol. 12; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Current Status and Future Prospects of Metal–Sulfur Batteries journal May 2019
Ni 3 S 2 anchored to N/S co-doped reduced graphene oxide with highly pleated structure as a sulfur host for lithium–sulfur batteries journal January 2020

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Related Subjects

25 ENERGY STORAGE
controlled solid-state reactions
electrochemical systems
lithium-sulfur battery
single-walled carbon nanotubes
sub-nanoscale confined sulfur