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

Abstract

Vanadium sulfide VS4 in the patronite mineral structure, is a linear chain compound comprising vanadium atoms coordinated by disulfide anions [S2]2–. 51V NMR shows that the material, despite having V formally in the d1 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 Å and 3.2 Å along the chains. Partial lithiation results in reduction of the disulfide ions to sulfide S2–, including via an internal redox process whereby an electron from V4+ is transferred to [S2]2– resulting in oxidation of V4+ to V5+ and reduction of the [S2]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. In conclusion, the unusual redox processes in this system are elucidated using amore » suite of short range characterization tools including 51V Nuclear Magnetic Resonance spectroscopy (NMR), S Kedge X-ray Absorption Near Edge Spectroscopy (XANES) and Pair Distribution Function (PDF) Analysis of X-ray data.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [5];  [5];  [6];  [7];  [1]
  1. Univ. of Cambridge (United Kingdom)
  2. Univ. of California, Santa Barbara, CA (United States)
  3. Ulsan National Inst. of Science and Technology (UNIST), Ulsan (Korea)
  4. Univ. of Oxford (United Kingdom)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  6. Univ. of California, Santa Barbara, CA (United States). Mitsubishi Chemicals Center for Advanced Materials Research Laboratory
  7. Ulsan National Inst. of Science and Technology (UNIST), Ulsan (Korea). Interdisciplinary School of Green Energy
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1254008
Grant/Contract Number:  
AC02-06CH11357; NSF CNS-0960316; DMR-1121053
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 26; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; lithium-ion battery; conversion mechanism; peierls distortion

Citation Formats

Britto, Sylvia, Leskes, Michal, Hua, Xiao, Hébert, Claire-Alice, Shin, Hyeon Suk, Clarke, Simon, Borkiewicz, Olaf, Chapman, Karena W., Seshadri, Ram, Cho, Jaephil, and Grey, Clare P. Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide. United States: N. p., 2015. Web. doi:10.1021/jacs.5b03395.
Britto, Sylvia, Leskes, Michal, Hua, Xiao, Hébert, Claire-Alice, Shin, Hyeon Suk, Clarke, Simon, Borkiewicz, Olaf, Chapman, Karena W., Seshadri, Ram, Cho, Jaephil, & Grey, Clare P. Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide. United States. https://doi.org/10.1021/jacs.5b03395
Britto, Sylvia, Leskes, Michal, Hua, Xiao, Hébert, Claire-Alice, Shin, Hyeon Suk, Clarke, Simon, Borkiewicz, Olaf, Chapman, Karena W., Seshadri, Ram, Cho, Jaephil, and Grey, Clare P. 2015. "Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide". United States. https://doi.org/10.1021/jacs.5b03395. https://www.osti.gov/servlets/purl/1254008.
@article{osti_1254008,
title = {Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide},
author = {Britto, Sylvia and Leskes, Michal and Hua, Xiao and Hébert, Claire-Alice and Shin, Hyeon Suk and Clarke, Simon and Borkiewicz, Olaf and Chapman, Karena W. and Seshadri, Ram and Cho, Jaephil and Grey, Clare P.},
abstractNote = {Vanadium sulfide VS4 in the patronite mineral structure, is a linear chain compound comprising vanadium atoms coordinated by disulfide anions [S2]2–. 51V NMR shows that the material, despite having V formally in the d1 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 Å and 3.2 Å along the chains. Partial lithiation results in reduction of the disulfide ions to sulfide S2–, including via an internal redox process whereby an electron from V4+ is transferred to [S2]2– resulting in oxidation of V4+ to V5+ and reduction of the [S2]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. In conclusion, the unusual redox processes in this system are elucidated using a suite of short range characterization tools including 51V Nuclear Magnetic Resonance spectroscopy (NMR), S Kedge X-ray Absorption Near Edge Spectroscopy (XANES) and Pair Distribution Function (PDF) Analysis of X-ray data.},
doi = {10.1021/jacs.5b03395},
url = {https://www.osti.gov/biblio/1254008}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 26,
volume = 137,
place = {United States},
year = {Mon Jun 08 00:00:00 EDT 2015},
month = {Mon Jun 08 00:00:00 EDT 2015}
}

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Works referencing / citing this record:

VS 4 ‐Decorated Carbon Nanotubes for Lithium Storage with Pseudocapacitance Contribution
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Structural characterization of an amorphous VS 4 and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy
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Natural abundance solid-state 33 S NMR study of NbS 3 : applications for battery conversion electrodes
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One-pot pyro synthesis of a nanosized-LiMn 2 O 4 /C cathode with enhanced lithium storage properties
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Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries
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Mechanical exfoliation and electrical characterization of a one-dimensional Nb 2 Se 9 atomic crystal
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Antisite occupation induced single anionic redox chemistry and structural stabilization of layered sodium chromium sulfide
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Synthesis of a one-dimensional atomic crystal of vanadium selenide (V 2 Se 9 )
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Exploring the bottlenecks of anionic redox in Li-rich layered sulfides
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Graphene Oxide-Template Controlled Cuboid-Shaped High-Capacity VS 4 Nanoparticles as Anode for Sodium-Ion Batteries
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Exfoliation and Characterization of V2Se9 Atomic Crystals
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Exfoliation and Characterization of V2Se9 Atomic Crystals
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