Visualizing Lithium-Ion Migration Pathways in Battery Materials

2013 ◽  
Vol 19 (46) ◽  
pp. 15535-15544 ◽  
Author(s):  
Mette Ø. Filsø ◽  
Michael J. Turner ◽  
Gerald V. Gibbs ◽  
Stefan Adams ◽  
Mark A. Spackman ◽  
...  
Keyword(s):  
Lithium Ion ◽  
Ion Migration ◽  
Battery Materials ◽  
Migration Pathways

Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Barbara Koch ◽  
Shiao Tong Kong ◽  
Özgül Gün ◽  
Hans-Jörg Deiseroth ◽  
Hellmut Eckert
Keyword(s):  
Solid Solutions ◽  
Lithium Ion ◽  
Ionic Mobility ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
Ion Migration ◽  
Iodide Ions ◽  
Nmr Study ◽  
Structural Configurations ◽  
Migration Pathways

Abstract A comprehensive multinuclear (7Li, 31P, 35Cl, 77Se, 79Br) nuclear magnetic resonance (NMR) study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically disordered solid solutions of composition Li6PS5−x Se x X (0 ≤ x ≤ 1, X = Cl, Br) with the Argyrodite structure. In contrast to the situation with the corresponding iodide homologs, there is no structural ordering between the 4a and 4c sites, with the halide ions occupying both of them with close to statistical probabilities. Nevertheless, throughout the composition range, the 16e Wyckoff sites of the Argyrodite structure are exclusively occupied by the chalcogen atoms, forming PY4 3− (Y = S, Se) tetrahedra, indicating the absence of P-halogen bonds. 31P magic-angle spinning (MAS)-NMR can serve to differentiate between the various possible PS4−n Se n 3− tetrahedral units in a quantitative fashion. Compared to the case of the anion-ordered Li6PS5−x Se x I solid solutions, the preference of P–S over P–Se bonding is significantly stronger, but it is weaker than in the halide free solid solutions Li7PS6−x Se x . Each individual PS4−n Se n 3− tetrahedron is represented by a peak cluster of up to five resonances, representing the five different configurations in which the PY4 3− ions are surrounded by the four closest chalcogenide and halide anions occupying the 4c sites; this distribution is close to statistical and can be used to deduce deviations of sample compositions from ideal stoichiometry. Non-linear 7Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS4−n Se n 3− ions (n ≤ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e., selenium-richer PY4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li+ ions to spend on average more time near them. Temperature dependent static 7Li NMR linewidths indicate higher mobility in the present systems than in the previously studied Li6PS5−x Se x I solid solutions. Unlike the situation in Li6PS5−x Se x I no rate distinction between intra-cage and inter-cage ionic motion is evident. Lithium ionic mobility increases with increasing selenium content. This effect can be attributed to the influences of higher anionic polarizability and a widening of the lithium ion migration pathways caused by lattice expansion. The results offer interesting new insights into the structure/ionic mobility correlations in this new class of compounds.

Lithium ion migration pathways in LiTi2(PO4)3 and related materials

1999 ◽  
Vol 86 (10) ◽  
pp. 5484-5491 ◽  
Author(s):  
Gerhard Nuspl ◽  
Tomonari Takeuchi ◽  
Armin Weiß ◽  
Hiroyuki Kageyama ◽  
Kazunari Yoshizawa ◽  
...  
Keyword(s):  
Lithium Ion ◽  
Ion Migration ◽  
Migration Pathways

Lithium ion migration pathways in Li3xLa2/3−x□1/3−2xTiO3

2012 ◽  
Vol 38 ◽  
pp. S467-S470 ◽  
Author(s):  
Dae-Hee Kim ◽  
Dae-Hyun Kim ◽  
Yong-Chan Jeong ◽  
Hwa-Il Seo ◽  
Yeong-Cheol Kim
Keyword(s):  
Lithium Ion ◽  
Ion Migration ◽  
Migration Pathways

scholarly journals First-Principles studies of silicon underpotential deposition on defective graphene and its relevance for lithium-ion battery materials

2016 ◽  
Vol 208 ◽  
pp. 92-101 ◽  
Author(s):  
M. Laura Urquiza ◽  
Manuel Otero ◽  
Guillermina L. Luque ◽  
Daniel Barraco ◽  
Ezequiel P.M. Leiva
Keyword(s):  
Lithium Ion Battery ◽  
First Principles ◽  
Lithium Ion ◽  
Underpotential Deposition ◽  
Battery Materials ◽  
Defective Graphene

Fast Lithium Ion Migration in Room Temperature LiBH4

2017 ◽  
Vol 121 (33) ◽  
pp. 17773-17779 ◽  
Author(s):  
Young-Su Lee ◽  
Young Whan Cho
Keyword(s):  
Room Temperature ◽  
Lithium Ion ◽  
Ion Migration

scholarly journals Diffusion Pathways and Activation Energies in Crystalline Lithium-Ion Conductors

2017 ◽  
Vol 231 (7-8) ◽  
Author(s):  
Dennis Wiedemann ◽  
Mazharul M. Islam ◽  
Thomas Bredow ◽  
Martin Lerch
Keyword(s):  
Scattering Length ◽  
Lithium Ion ◽  
Research Unit ◽  
Energy Storage Materials ◽  
Activation Barriers ◽  
Ion Migration ◽  
Density Maps ◽  
Lithium Transport ◽  
Lithium Ion Conductors ◽  
Ion Conductors

AbstractGeometric information about ion migration (diffusion pathways) and knowledge about the associated energy landscape (migration activation barriers) are essential cornerstones for a comprehensive understanding of lithium transport in solids. Although many lithium-ion conductors are discussed, developed, and already used as energy-storage materials, fundamental knowledge is often still lacking. In this microreview, we give an introduction to the experimental and computational methods used in our subproject within the research unit FOR 1277, “Mobility of Lithium Ions in Solids (molife)”. These comprise, amongst others, neutron diffraction, topological analyses (procrystal-void analysis and Voronoi–Dirichlet partitioning), examination of scattering-length density maps reconstructed

scholarly journals The inverse perovskite BaLiF3: single-crystal neutron diffraction and analyses of potential ion pathways

2018 ◽  
Vol 74 (6) ◽  
pp. 643-650 ◽  
Author(s):  
Dennis Wiedemann ◽  
Falk Meutzner ◽  
Oscar Fabelo ◽  
Steffen Ganschow
Keyword(s):  
High Temperature ◽  
Neutron Diffraction ◽  
Scattering Length ◽  
Temperature Structure ◽  
Luminescent Materials ◽  
Lithium Ions ◽  
Ion Migration ◽  
Mobile Species ◽  
Tolerance Factors ◽  
Migration Pathways

Doped barium lithium trifluoride has attracted attention as component for scintillators, luminescent materials and electrodes. With lithium and fluoride, it contains two possibly mobile species, which may account for its ionic conductivity. In this study, neutron diffraction on oxide-containing BaLiF3 single-crystals is performed at up to 636.2°C. Unfortunately, ion-migration pathways could not be mapped by modelling anharmonic ion displacement or by inspecting the scattering-length density that was reconstructed via maximum-entropy methods. However, analyses of the topology and bond-valence site energies derived from the high-temperature structure reveal that the anions can migrate roughly along the edges of the LiF6 coordination octahedra with an estimated migration barrier of ∼0.64 eV (if a vacancy permits), whereas the lithium ions are confined to their crystallographic positions. This finding is not only valid for the title compound but for ion migration in all perovskites with Goldschmidt tolerance factors near unity.

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