Extremely slow Li ion dynamics in monoclinic Li2TiO3—probing macroscopic jump diffusion via7Li NMR stimulated echoes

Ruprecht, Benjamin; Wilkening, Martin; Uecker, R.; Heitjans, Paul

doi:10.1039/c2cp41662j

Cited by 45 publications

(55 citation statements)

References 66 publications

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“…While ion transport in nanocrystalline, defect-rich LiMO 3 (M = Ta, Nb) has extensively been studied previously [3][4][5], little is known about Li + dynamics in, e.g., LiAlO 2 [6] or the various Li-bearing titanates such as Li 2 TiO 3 [7] if these oxides are present in an amorphous or nanocrystalline form [8,9]. Here, we used high-energy ball milling to prepare phase pure nanocrystalline Li 2 TiO 3 starting from a commercially available coarse-grained material characterized by μm-sized crystallites.…”

Section: Introductionmentioning

confidence: 99%

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃

Brandstätter¹,

Wohlmuth²,

Bottke³

et al. 2015

Zeitschrift Für Physikalische Chemie

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The monoclinic polymorph of Li 2 TiO 3 (β-form) is known to be a relatively poor Li ion conductor. Up to now, no information is available on how the ion transport properties change when going from well-ordered crystalline Li 2 TiO 3 to a structurally disordered form with the same chemical composition. Here, we used high-energy ball milling to prepare nanocrystalline, defect-rich Li 2 TiO 3 ; ion dynamics have been studied via impedance spectroscopy. It turned out that ball milling offers the possibility to enhance long-range ion transport in the oxide by approximately 3 orders of magnitude. Its effect on the oxide ceramic is two-fold: besides the introduction of a large number of defects, the originally μm-sized crystallites are decreased to crystallites with a mean diameter of less than 50 nm. This process is accompanied by a mechanically induced phase transformation towards the α-form of Li 2 TiO 3 ; besides that, a significant amount of amorphous materials is produced during milling. Structural disorder in nanocrystalline as well as amorphous Li 2 TiO 3 is anticipated to play the capital role in governing Li ion dynamics of the sample finally obtained.

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Section: Introductionmentioning

confidence: 99%

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃

Brandstätter¹,

Wohlmuth²,

Bottke³

et al. 2015

Zeitschrift Für Physikalische Chemie

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“…By sensing the dipolar-magnetic or quadrupolar-electric fluctuations as a function of temperature, through NMR relaxation techniques bulk ion dynamics are probed that shed light on the elementary steps governing ion hopping. Moreover, in ideal cases NMR also allows to draw conclusions about the underlying motional correlation functions [68][69][70][71][72]. In contrast to impedance or conductivity measurements no post-preparation of the synthesized powder, i.e., pressing of dense pellets, applying of electrodes, is necessary.…”

Section: Introductionmentioning

confidence: 99%

Ion dynamics in solid electrolytes for lithium batteries

et al. 2017

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All-solid-state batteries with ceramic electrolytes and lithium metal anodes represent an attractive alternative to conventional ion battery systems. Conventional batteries still rely on flammable liquids as electronic insulators. Despite the great efforts reported over the last years, the optimum solid electrolyte has, however, not been found yet. One of the most important properties which decides whether a ceramic is useful to work as electrolyte is ionic transport. The various time-domain nuclear magnetic resonance (NMR) techniques might help characterize and select the most suitable candidates. Together with conductivity measurements it is possible to analyze ion dynamics on different length-scales, i.e., to differentiate between local, within-site hopping processes from long-range ion transport. The latter needs to be sufficiently fast in the ceramic, in the best case competing with that of liquid electrolytes. In addition to conductivity spectroscopy, NMR can help understand the relationship between local structure and dynamic parameters. Besides information on activation energies and jump rates the data also contain suggestions about the relevant elementary steps of ion hopping and, thus, Support by the Deutsche Forschungsgemeinschaft (DFG) is highly appreciated (FOR 1277 diffusion pathways through the crystal lattice. Recent progress in characterizing ion dynamics in ceramic electrolytes by NMR relaxometry will be briefly reviewed. Focus is put on presently discussed solid electrolytes such as garnets, phosphates and sulfides, which have so far been studied in our lab.

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“…, corresponding to slow motion in the lowtemperature regime [42,43]. Static 7 Li NMR spectra of most materials suffer from strong dipolar broadening due to the high dipolar moment of the 7 Li nucleus.…”

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confidence: 99%

Slow Lithium Transport in Metal Oxides on the Nanoscale

Uhlendorf

Ruprecht

Witt

et al. 2017

Zeitschrift Für Physikalische Chemie

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This article reports on Li self-diffusion in lithium containing metal oxide compounds. Case studies on LiNbO 3 , Li 3 NbO 4 , LiTaO 3 , LiAlO 2 , and LiGaO 2 are presented. The focus is on slow diffusion processes on the nanometer scale investigated by macroscopic tracer methods (secondary ion mass spectrometry, neutron reflectometry) and microscopic methods (nuclear magnetic resonance spectroscopy, conductivity spectroscopy) in comparison. Special focus is on the influence of structural disorder on diffusion.

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Extremely slow Li ion dynamics in monoclinic Li2TiO3—probing macroscopic jump diffusion via7Li NMR stimulated echoes

Cited by 45 publications

References 66 publications

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃

Ion dynamics in solid electrolytes for lithium batteries

Slow Lithium Transport in Metal Oxides on the Nanoscale

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Extremely slow Li ion dynamics in monoclinic Li2TiO3—probing macroscopic jump diffusion via7Li NMR stimulated echoes

Cited by 45 publications

References 66 publications

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li2TiO3

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li2TiO3

Ion dynamics in solid electrolytes for lithium batteries

Slow Lithium Transport in Metal Oxides on the Nanoscale

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Product

Resources

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Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃

Li Ion Dynamics in Nanocrystalline and Structurally Disordered Li₂TiO₃