Solid State Ionics, volume 362, pages 115585
Lithium-ion diffusivity in complex hydrides: Pulsed-field-gradient NMR studies of LiLa(BH4)3Cl, Li3(NH2)2I and Li-1-CB9H10
Skripov Alexander
1
,
Majer G.
2
,
Babanova Olga A
1, 3
,
Skoryunov Roman
1
,
Soloninin A.V.
1
,
Ley M B
4
,
Orimo Shin-ichi
5
,
Udovic Terrence John
6, 7
2
Max Planck Institute for Intelligent Systems 70569 Stuttgart Germany
|
5
WPI-Advanced Institute for Materials Research Tohoku University Sendai 980–8577 Japan
|
6
Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742, USA.
|
7
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA.
|
Publication type: Journal Article
Publication date: 2021-04-01
General Chemistry
Condensed Matter Physics
General Materials Science
Abstract
The bimetallic borohydride-chloride LiLa(BH 4 ) 3 Cl, the lithium amide-iodide Li 3 (NH 2 ) 2 I, and the lithium monocarba- closo -decaborate Li-1-CB 9 H 10 represent complex hydrides showing superionic conductivity at room temperature or slightly above it. To study the Li-ion diffusivity that is closely related to the ionic conductivity, we have measured the diffusion coefficients of Li + cations in these compounds using the pulsed-field-gradient (PFG) spin-echo technique over the temperature range of 298–403 K. The experiments have revealed fast Li + diffusivities in all these complex hydrides: at 400 K, the measured diffusion coefficients exceed 10 −7 cm 2 /s for LiLa(BH 4 ) 3 Cl, 5 × 10 −8 cm 2 /s for Li 3 (NH 2 ) 2 I, and 10 −6 cm 2 /s for Li-1-CB 9 H 10 . For LiLa(BH 4 ) 3 Cl and Li 3 (NH 2 ) 2 I, the diffusion coefficients are found to follow the Arrhenius behavior over the entire temperature ranges studied with the activation energies of 268(6) meV and 224(6) meV, respectively. For Li-1-CB 9 H 10 , the Arrhenius behavior with the activation energy of 265(6) meV is observed in the disordered high-temperature polymorph (360–403 K), whereas below 360 K the measured diffusivity drops significantly due to the transition to the ordered phase. Comparison of the measured Li + diffusion coefficients with the ionic conductivity results and the data on the cation and anion jump rates provides new insights into the unusual dynamical properties of these superionic materials. • High Li + diffusivity is revealed in three complex hydrides. • The measured activation energies for Li + diffusion are in the range of 224–268 meV. • For LiLa(BH 4 ) 3 Cl, the Li + diffusion path includes two types of interstitial sites. • The order-disorder transition in LiCB 9 H 10 leads to strong changes in Li + diffusivity. • In the disordered phase of LiCB 9 H 10 , the measured diffusivity is anomalously high.
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Skripov A. et al. Lithium-ion diffusivity in complex hydrides: Pulsed-field-gradient NMR studies of LiLa(BH4)3Cl, Li3(NH2)2I and Li-1-CB9H10 // Solid State Ionics. 2021. Vol. 362. p. 115585.
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Skripov A., Majer G., Babanova O. A., Skoryunov R., Soloninin A., Ley M. B., Jensen T. R., Orimo S., Udovic T. J. Lithium-ion diffusivity in complex hydrides: Pulsed-field-gradient NMR studies of LiLa(BH4)3Cl, Li3(NH2)2I and Li-1-CB9H10 // Solid State Ionics. 2021. Vol. 362. p. 115585.
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TY - JOUR
DO - 10.1016/j.ssi.2021.115585
UR - https://doi.org/10.1016%2Fj.ssi.2021.115585
TI - Lithium-ion diffusivity in complex hydrides: Pulsed-field-gradient NMR studies of LiLa(BH4)3Cl, Li3(NH2)2I and Li-1-CB9H10
T2 - Solid State Ionics
AU - Skripov, Alexander
AU - Majer, G.
AU - Babanova, Olga A
AU - Skoryunov, Roman
AU - Soloninin, A.V.
AU - Ley, M B
AU - Jensen, Torben René
AU - Orimo, Shin-ichi
AU - Udovic, Terrence John
PY - 2021
DA - 2021/04/01 00:00:00
PB - Elsevier
SP - 115585
VL - 362
SN - 0167-2738
ER -
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@article{2021_Skripov,
author = {Alexander Skripov and G. Majer and Olga A Babanova and Roman Skoryunov and A.V. Soloninin and M B Ley and Torben René Jensen and Shin-ichi Orimo and Terrence John Udovic},
title = {Lithium-ion diffusivity in complex hydrides: Pulsed-field-gradient NMR studies of LiLa(BH4)3Cl, Li3(NH2)2I and Li-1-CB9H10},
journal = {Solid State Ionics},
year = {2021},
volume = {362},
publisher = {Elsevier},
month = {apr},
url = {https://doi.org/10.1016%2Fj.ssi.2021.115585},
pages = {115585},
doi = {10.1016/j.ssi.2021.115585}
}
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