This title appears in the Scientific Report :
2024
Please use the identifier:
http://dx.doi.org/10.1039/D3CP05089K in citations.
Interstitial or interstitialcy: effect of the cation size on the migration mechanism in NaSICON materials
Interstitial or interstitialcy: effect of the cation size on the migration mechanism in NaSICON materials
Sodium superionic conductors (NaSICONs) with general formula NaM2A3O12 have attracted significant attention as solid electrolytes for all solid-state batteries owing to their remarkable room temperature ionic conductivity in the order of 10−3 S cm−1. Their flexible structural framework, which allows...
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Personal Name(s): | Schuett, Judith |
---|---|
Schillings, Johanna / Neitzel-Grieshammer, Steffen (Corresponding author) | |
Contributing Institute: |
Helmholtz-Institut Münster Ionenleiter für Energiespeicher; IEK-12 |
Published in: | Physical chemistry, chemical physics, 26 (2024) 3, S. 2190 - 2204 |
Imprint: |
Cambridge
RSC Publ.
2024
|
DOI: |
10.1039/D3CP05089K |
Document Type: |
Journal Article |
Research Program: |
Bestimmung der ionischen Leitfähigkeit von kationenleitenden Elektrolyten mittels Kinetik Monte Carlo Simulationen Fundamentals and Materials |
Publikationsportal JuSER |
Sodium superionic conductors (NaSICONs) with general formula NaM2A3O12 have attracted significant attention as solid electrolytes for all solid-state batteries owing to their remarkable room temperature ionic conductivity in the order of 10−3 S cm−1. Their flexible structural framework, which allows the incorporation of various aliovalent cations, affects the Na+ ion transport. However, establishing a straightforward correlation between Na+ mobility and NaSICON composition proves challenging due to competing influences such as framework alteration and stoichiometric changes of the cation substituents and thus the mobile Na+ ions. Therefore, we systematically investigate the NaSICON system across various Na1+xM2SixP3−xO12 compositions. We unravel and examine independently two key aspects impacting the Na+ ion transport in NaSICONs: structural factors determined by introduced M4+ framework cations and the substitution level (x). By employing DFT calculations, we explore the interstitial- and interstitialcy-like migration mechanisms, revealing that these mechanisms and the associated migration energies are primarily influenced by metastable transient states traversed during the Na+ ion migration. The stability of these transient states, in turn, depends on the spatial arrangement of the Na+ ions, the size of the M4+ cations defining the structural framework, and x. This study enhances our fundamental understanding of Na+ ion migration within NaSICONs across a wide range of compositions. The findings offer valuable insights into the microscopic aspects of NaSICON materials and provide essential guidance for prospective studies in this field. |