BROWSE

Related Researcher

Author's Photo

Cho, Jaephil
Nano Energy Storage Materials Lab (NESM)
Research Interests
  • Li-ion battery, metal-air battery, redox-flow battery, flexible battery .

ITEM VIEW & DOWNLOAD

Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

Cited 0 times inthomson ciCited 0 times inthomson ci
Title
Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide
Author
Britto, SylviaLeskes, MichalHua, XiaoHebert, Claire-AliceShin, Hyeon SukClarke, SimonBorkiewicz, OlafChapman, Karena W.Seshadri, RamCho, JaephilGrey, Clare P.
Issue Date
2015-07
Publisher
AMER CHEMICAL SOC
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.137, no.26, pp.8499 - 8508
Abstract
Vanadium sulfide VS4 in the patronite mineral structure is a linear chain compound comprising vanadium atoms coordinated by disulfide anions [S-2](2-). V-51 NMR shows that the material, despite having V formally in the d(1) configuration, is diamagnetic, suggesting potential dimerization through metal metal bonding associated with a Peierls distortion of the linear chains. This is supported by density functional calculations, and is also consistent with the observed alternation in V V distances of 2.8 and 3.2 angstrom along the chains. Partial lithiation results in reduction of the disulfide ions to sulfide S2-, via an internal redox process whereby an electron from V4+ is transferred to [S-2](2-) in oxidation of V4+ to V5+ and reduction of the [S-2](2-) to S2- to form Li3VS4 containing tetrahedral [VS4](3-) anions. On further lithiation this is followed by reduction of the V5+ in Li3VS4 to form Li3+xVS4 (x = 0.5-1), a mixed valent V4+/V5+ compound. Eventually reduction to Li2S plus elemental V occurs. Despite the complex redox processes involving both the cation and the anion occurring in this material, the system is found to be partially reversible between 0 and 3 V. The unusual redox processes in this system are elucidated using a suite of short-range characterization tools including V-51 nuclear magnetic resonance spectroscopy (NMR), S K-edge X-ray absorption near edge spectroscopy (XANES), and pair distribution function (PDF) analysis of X-ray data
URI
https://scholarworks.unist.ac.kr/handle/201301/16408
URL
http://pubs.acs.org/doi/abs/10.1021/jacs.5b03395
DOI
10.1021/jacs.5b03395
ISSN
0002-7863
Appears in Collections:
PHY_Journal Papers
ECHE_Journal Papers
Files in This Item:
There are no files associated with this item.

find_unist can give you direct access to the published full text of this article. (UNISTARs only)

Show full item record

qrcode

  • mendeley

    citeulike

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

MENU