TY - JOUR
T1 - Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide
AU - Britto, Sylvia
AU - Leskes, Michal
AU - Hua, Xiao
AU - Hebert, Claire-Alice
AU - Shin, Hyeon Suk
AU - Clarke, Simon
AU - Borkiewicz, Olaf
AU - Chapman, Karena W.
AU - Seshadri, Ram
AU - Cho, Jaephil
AU - Grey, Clare P.
N1 - S.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.
PY - 2015/7/8
Y1 - 2015/7/8
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84936818348&partnerID=8YFLogxK
U2 - https://doi.org/10.1021/jacs.5b03395
DO - https://doi.org/10.1021/jacs.5b03395
M3 - مقالة
SN - 0002-7863
VL - 137
SP - 8499
EP - 8508
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 26
ER -