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Issue 25, 2007
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The mechanism of Li-ion transport in the garnet Li5La3Nb2O12

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We present a detailed study on the exact location and dynamics of Li ions in the garnet-type material Li5La3Nb2O12 employing advanced solid state NMR strategies. Applying temperature-dependent 7Li-NMR, 6Li-MAS-NMR, 6Li-{7Li}-CPMAS-NMR, 6Li-{7Li}-CPMAS-REDOR-NMR as well as 2D-6Li-{7Li}-CPMAS-Exchange-NMR spectroscopy, we were able to quantify the distribution of the Li cations among the various possible sites within the garnet-type structure and to identify intrinsic details of Li migration. The results indicate a sensitive dependence of the distribution of Li cations among the tetrahedral and octahedral sites on the temperature of the final annealing process. This distribution profoundly affects the mobility of the Li cations within the garnet-type framework structure. Extended Li mobility at ambient temperature is only possible if the majority of the Li cations is accommodated in the octahedral sites, as observed for the sample annealed at 900 °C. Octahedrally-coordinated Li cations could be identified as the mobile Li species, whereas the tetrahedral sites seem to act as a trap for the Li cations, rendering the tetrahedrally-coordinated Li cations immobile on the time scale of the NMR experiments.

Graphical abstract: The mechanism of Li-ion transport in the garnet Li5La3Nb2O12

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Publication details

The article was received on 02 Mar 2007, accepted on 02 May 2007 and first published on 18 May 2007

Article type: Paper
DOI: 10.1039/B703179C
Citation: Phys. Chem. Chem. Phys., 2007,9, 3298-3303
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    The mechanism of Li-ion transport in the garnet Li5La3Nb2O12

    L. van Wüllen, T. Echelmeyer, H. Meyer and D. Wilmer, Phys. Chem. Chem. Phys., 2007, 9, 3298
    DOI: 10.1039/B703179C

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