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Exploring the Effect of Anion Substitution on the Solid Ionic Conductor NaTaCl6
Vasiliki Faka1, Bibek Samanta2,3, Iven Koers1
1Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstraße 28/30, 48149 Münster, Germany.
Bromide substitution in sodium tantalum chloride solid electrolytes decreases ionic conductivity, unlike in lithium analogs. This highlights structural differences impacting sodium-ion transport for solid-state batteries.
Area of Science:
- Solid-state ionics
- Materials science
- Electrochemistry
Background:
- Isovalent anion substitution significantly impacts ionic conductivity in solid conductors.
- Sodium-ion batteries are gaining attention, but anion substitution in sodium chlorides is understudied.
- Lithium halide conductors show promise, but direct transfer of principles to sodium systems is uncertain.
Purpose of the Study:
- Investigate the effect of bromide (Br-) anion substitution in NaTaCl6 perovskite-related compounds.
- Understand the role of cation vacancies in accommodating bromide substitution.
- Analyze the impact of Br- substitution on sodium-ion (Na+) transport properties.
Main Methods:
- Rietveld refinements of X-ray diffraction data to analyze structural changes.
- Nuclear magnetic resonance (NMR) spectroscopy to probe Na+ coordination.
- Impedance spectroscopy to measure ionic conductivity.
Main Results:
- Complete solid solutions were achieved with Br- substitution, facilitated by cation vacancies.
- Unit cell volume increased, and Na+ coordination changed with increasing Br- content.
- Room-temperature ionic conductivity decreased with Br- substitution, contrasting with lithium systems.
Conclusions:
- Structural factors influence Na+ transport differently compared to Li+ transport.
- Direct application of Li+ conductor design principles to Na+ systems requires caution.
- Further research is needed to optimize sodium halide solid electrolytes for Na+ solid-state batteries.
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