PMID- 30247879
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20191120
IS  - 1936-086X (Electronic)
IS  - 1936-0851 (Linking)
VI  - 12
IP  - 10
DP  - 2018 Oct 23
TI  - Confined Lithium-Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal 
      Enhanced Electrochemical Reactivity.
PG  - 9775-9784
LID - 10.1021/acsnano.7b08778 [doi]
AB  - 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.
FAU - Fu, Chengyin
AU  - Fu C
FAU - Oviedo, M Belen
AU  - Oviedo MB
AUID- ORCID: 0000-0002-3200-9929
FAU - Zhu, Yihan
AU  - Zhu Y
AD  - Department of Chemical Engineering , Zhejiang University of Technology , Hangzhou 
      310014 , China.
FAU - von Wald Cresce, Arthur
AU  - von Wald Cresce A
AD  - United States Army Research Laboratory , Adelphi , Maryland 20783 , United 
      States.
FAU - Xu, Kang
AU  - Xu K
AD  - United States Army Research Laboratory , Adelphi , Maryland 20783 , United 
      States.
FAU - Li, Guanghui
AU  - Li G
FAU - Itkis, Mikhail E
AU  - Itkis ME
AUID- ORCID: 0000-0003-2447-2267
FAU - Haddon, Robert C
AU  - Haddon RC
FAU - Chi, Miaofang
AU  - Chi M
AUID- ORCID: 0000-0003-0764-1567
AD  - Center for Nanophase Materials Sciences , Oak Ridge National Laboratory , Oak 
      Ridge , Tennessee 37831 , United States.
FAU - Han, Yu
AU  - Han Y
AUID- ORCID: 0000-0003-1462-1118
AD  - Chemical Science Program , King Abdullah University of Science and Technology , 
      Thuwal 23955 , Kingdom of Saudi Arabia.
FAU - Wong, Bryan M
AU  - Wong BM
AUID- ORCID: 0000-0002-3477-8043
FAU - Guo, Juchen
AU  - Guo J
AUID- ORCID: 0000-0001-9829-1202
LA  - eng
PT  - Journal Article
DEP - 20180927
PL  - United States
TA  - ACS Nano
JT  - ACS nano
JID - 101313589
OTO - NOTNLM
OT  - controlled solid-state reactions
OT  - electrochemical systems
OT  - lithium-sulfur battery
OT  - single-walled carbon nanotubes
OT  - sub-nanoscale confined sulfur
EDAT- 2018/09/25 06:00
MHDA- 2018/09/25 06:01
CRDT- 2018/09/25 06:00
PHST- 2018/09/25 06:00 [pubmed]
PHST- 2018/09/25 06:01 [medline]
PHST- 2018/09/25 06:00 [entrez]
AID - 10.1021/acsnano.7b08778 [doi]
PST - ppublish
SO  - ACS Nano. 2018 Oct 23;12(10):9775-9784. doi: 10.1021/acsnano.7b08778. Epub 2018 
      Sep 27.