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dc.contributor.authorBritto, Sylvia
dc.contributor.authorLeskes, Michal
dc.contributor.authorHua, Xiao
dc.contributor.authorHébert, Claire-Alice
dc.contributor.authorShin, Hyeon Suk
dc.contributor.authorClarke, Simon
dc.contributor.authorBorkiewicz, Olaf
dc.contributor.authorChapman, Karena W.
dc.contributor.authorSeshadri, Ram
dc.contributor.authorCho, Jaephil
dc.contributor.authorGrey, Clare P.
dc.date.accessioned2015-07-09T16:09:06Z
dc.date.available2015-07-09T16:09:06Z
dc.date.issued2015-06-08
dc.identifier.citationBritto et al. Journal of the American Chemical Society (2015), 137 (26), pp. 8499-8508 DOI: 10.1021/jacs.5b03395en
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/248880
dc.descriptionThis is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/jacs.5b03395en
dc.description.abstractVanadium sulfide VS_4 in the patronite mineral structure is a linear chain compound comprising vanadium atoms coordinated by disulfide anions [S_2]^2–. 51V 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 Å along the chains. Partial lithiation results in reduction of the disulfide ions to sulfide S^2–, via an internal redox process whereby an electron from V^4+ is transferred to [S_2]^2– resulting in oxidation of V^4+ to V^5+ and reduction of the [S_2]^2– to S^2– to form Li_3VS_4 containing tetrahedral [VS_4]^3– anions. On further lithiation this is followed by reduction of the V^5+ in Li_3VS_4 to form Li(_3+x)VS_4 (x = 0.5–1), a mixed valent V^4+/V^5+ compound. Eventually reduction to Li_2S 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 51V 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.en
dc.description.sponsorshipS.B. acknowledges Schlumberger Stichting Fund and European Research Council (EU ERC) for funding. J.C. thanks BK21 plus project of Korea. We thank Phoebe Allan and Andrew J. Morris, University of Cambridge, for useful discussions. We also thank Trudy Bolin and Tianpin Wu of Beamline 9-BM, Argonne National Laboratory, for help with XANES measurements. The DFT calculations were performed at the UCSB Center for Scientific Computing at UC Santa Barbara, supported by the California Nanosystems Institute (NSF CNS-0960316), Hewlett-Packard, and the Materials Research Laboratory (DMR-1121053). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.en
dc.language.isoenen
dc.publisherACSen
dc.titleMultiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfideen
dc.typeArticleen
dc.type.versionaccepted versionen
prism.endingPage8508
prism.issueIdentifier26
prism.publicationDate2015
prism.publicationNameJournal of the American Chemical Society
prism.startingPage8499
prism.volume137
rioxxterms.versionofrecord10.1021/jacs.5b03395
rioxxterms.freetoread.startdate2016-06-08


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