Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 26, Pages 8499-8508Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b03395
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Funding
- Schlumberger Stichting Fund
- European Research Council (EU ERC)
- California Nanosystems Institute [NSF CNS-0960316]
- Hewlett-Packard
- Materials Research Laboratory [DMR-1121053]
- DOE Office of Science [DE-AC02-06CH11357]
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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.
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