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Ionic Pathways in Li13Si4 investigated by (6)Li and (7)Li solid state NMR experiments
Sven Dupke1, Thorsten Langer2, Florian Winter2
1Institut für Physikalische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany.
Solid State Nuclear Magnetic Resonance
|December 20, 2014
Summary
Lithium ion dynamics in lithium silicide (Li13Si4) reveal preferred transfer pathways and varying mobilities. Lithium ions near isolated silicon anions show lower mobility compared to those near silicon dumbbells.
Area of Science:
- Solid-state chemistry
- Materials science
- Nuclear magnetic resonance spectroscopy
Background:
- Lithium silicides are promising materials for energy storage applications.
- Understanding lithium ion dynamics is crucial for optimizing their performance.
Purpose of the Study:
- To investigate the local environments and dynamics of lithium ions in Li13Si4.
- To elucidate preferred ionic transfer pathways and factors influencing lithium mobility.
Main Methods:
- Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, including (6)Li MAS-NMR and (7)Li spin-lattice relaxation time measurements.
- (7)Li 2D exchange NMR experiments were conducted as a function of mixing time.
- Variable temperature experiments were employed to determine activation energies for ion transfer.
Main Results:
- Distinct differences in activation energies for lithium ion transfer between various sites were observed.
- A clear hierarchy of lithium ion mobility was established: Li6/Li7 > Li5 > Li1 > Li4 > Li2/Li3.
- Ionic transfer is more facile within the z=0.5 plane than the z=0 plane, with Li1/Li5 exchange facilitating inter-plane transfer.
Conclusions:
- The study provides a comprehensive understanding of lithium ion transfer pathways in Li13Si4.
- Lithium ion mobility is influenced by coordinating silicide anions and inter-lithium distances.
- Ions interacting with isolated Si(4-) anions exhibit lower mobility than those coordinated by Si2(6-) dumbbells.
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