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Main Title: Lithium diffusion pathways in 3R-LixTiS2: a combined neutron diffraction and computational study
Author(s): Wiedemann, Dennis
Islam, Mazharul M.
Nakhal, Suliman
Senyshyn, Anatoliy
Bredow, Thomas
Lerch, Martin
Type: Article
Abstract: Layered lithium transition-metal sulfides have long been discussed as early electrode materials for lithium-ion batteries. However, fundamental knowledge of lithium-ion migration in these solids is still lacking. In this study, we report on the diffusion dynamics in lithium-deficient high-temperature polymorphs of lithium titanium sulfides (3R-LixTiS2; x = 0.7, 0.9) as analyzed using powder neutron diffractometry and density functional theory (DFT) climbing-image nudged-elastic-band (cNEB) calculations. Two classes of probable migration pathways have been identified from the scattering-length density distributions (filtered using the maximum-entropy method [MEM]) and the probability density functions (PDFs, modeled from anharmonic Debye-Waller factors): direct diffusion in the (001) plane as the major mechanism and indirect diffusion through adjacent tetrahedral voids as a minor mechanism. Calculated activation barriers agree well with one-particle potentials (OPPs) derived from measurements for Li0.7TiS2 (0.484[14] and 0.88[4] eV) but deviate for Li0.9TiS2. The discrepancy at low defect concentration is attributed to the failure of the OPP derivation and the different nature of the methods (space-time averaged vs individual-ion perspective). This work elucidates the pathways of lithium-ion diffusion in 3R-LixTiS2 and points out pitfalls in established experimental/computational methods.
Issue Date: 2015
Date Available: 13-Sep-2016
Language Code: en
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, FOR 1277, Mobilität von Lithiumionen in Festkörpern (molife)
Journal Title: Journal of Physical Chemistry C
Publisher: American Chemical Society
Volume: 119
Issue: 21
Publisher DOI: 10.1021/acs.jpcc.5b01166
Page Start: 11370
Page End: 11381
EISSN: 1932-7455
ISSN: 1932-7447
TU Affiliation(s): Fak. 2 Mathematik und Naturwissenschaften » Inst. Chemie » FG Anorganische Chemie - Festkörper- und Materialchemie
Appears in Collections:Technische Universität Berlin » Publications

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