Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3

Edda Winter; Philipp Seipel; Tatiana Zinkevich; Sylvio Indris; Bambar Davaasuren; Frank Tietz; Michael Vogel

doi:10.1515/zpch-2021-3109

Published by De Gruyter (O) October 11, 2021

Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li_1.5Al_0.5Ti_1.5(PO₄)₃

Edda Winter , Philipp Seipel , Tatiana Zinkevich , Sylvio Indris , Bambar Davaasuren , Frank Tietz and Michael Vogel

From the journal Zeitschrift für Physikalische Chemie

https://doi.org/10.1515/zpch-2021-3109

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Abstract

Various nuclear magnetic resonance (NMR) methods are combined to study the structure and dynamics of Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) samples, which were obtained from sintering at various temperatures between 650 and 900 °C. ⁶Li, ²⁷Al, and ³¹P magic angle spinning (MAS) NMR spectra show that LATP crystallites are better defined for higher calcination temperatures. Analysis of ⁷Li spin-lattice relaxation and line-shape changes indicates the existence of two species of lithium ions with clearly distinguishable jump dynamics, which can be attributed to crystalline and amorphous sample regions, respectively. An increase of the sintering temperature leads to higher fractions of the fast lithium species with respect to the slow one, but hardly affects the jump dynamics in either of the phases. Specifically, the fast and slow lithium ions show jumps in the nanoseconds regime near 300 and 700 K, respectively. The activation energy of the hopping motion in the LATP crystallites amounts to ca. 0.26 eV. ⁷Li field-gradient diffusometry reveals that the long-range ion migration is limited by the sample regions featuring slow transport. The high spatial resolution available from the high static field gradients of our setup allows the observation of the lithium ion diffusion inside the small (<100 nm) LATP crystallites, yielding a high self-diffusion coefficient of D = 2 × 10⁻¹² m²/s at room temperature.

Keywords: field-gradient NMR; lithium ion dynamics; NMR spectroscopy; solid electrolytes; spin-lattice relaxation

Corresponding author: Michael Vogel, Institute for Condensed Matter Physics, Technische Universität Darmstadt, Hochschulstr., 6, D-64289 Darmstadt, Germany, E-mail: michael.vogel@physik.tu-darmstadt.de

Dedicated to Paul Heitjans on the occasion of his 75th birthday. Edda Winter and Philipp Seipel contributed equally to this work.

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-08-11

Accepted: 2021-09-15

Published Online: 2021-10-11

Published in Print: 2022-06-27

Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li_1.5Al_0.5Ti_1.5(PO₄)₃

Abstract

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