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Na4-Sn2-SbGe5O16, an Air-Stable Solid-State Na-Ion Conductor
Sergei Novikov1, Christopher J Franko1, Mengyang Cui1
1Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4M1, Canada.
Inorganic Chemistry
|September 18, 2023
Summary
This study enhances sodium-ion conductivity in Na4Sn2Ge5O16 by substituting tin with antimony. The resulting Na3.8Sn1.8Sb0.2Ge5O16 shows improved ionic conductivity, paving the way for better solid electrolytes.
Area of Science:
- Solid-state chemistry
- Materials science
- Electrochemistry
Background:
- The Na4Sn2Ge5O16 crystal structure was determined using single-crystal X-ray diffraction.
- Large displacement parameters of sodium (Na) atoms indicated potential for Na+ ionic conductivity.
Purpose of the Study:
- To enhance Na+ mobility in Na4Sn2Ge5O16 by creating Na deficiencies.
- To investigate the effect of Sn4+ substitution by Sb5+ on ionic conductivity.
Main Methods:
- Solid-state synthesis of Na4-xSbxSn2-xGe5O16 (x = 0-0.35) samples.
- Electrical impedance spectroscopy (EIS) measurements from 25-200 °C.
- Calculation of Na+ migration pathways using the bond-valence energy landscape (BVEL) approach.
- Solid-state 23Na and 119Sn nuclear magnetic resonance (NMR) spectroscopy.
Main Results:
- The highest ionic conductivity of 1.6 mS cm-1 at 200 °C was achieved for Na3.8Sn1.8Sb0.2Ge5O16.
- Calculations revealed 2D conductivity channels with low energy barriers (approx. 0.4 eV).
- NMR studies showed faster Na+ exchange between sites in the Sb-doped sample compared to the pristine phase.
Conclusions:
- Partial substitution of Sn4+ with Sb5+ effectively enhances Na+ ionic conductivity in the Na4Sn2Ge5O16 framework.
- The material exhibits promising properties for solid electrolyte applications.
- Understanding Na+ migration pathways is crucial for designing advanced ionic conductors.
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