High Sodium-Ion Conductivity in Interlocked Quaternary Chalcogenides Built with Supertetrahedral Building Units

Abstract

Herein, we report the syntheses, structure, Na-ion conductivity, and theoretical investigation of two moisture stable quaternary compounds, Na3ZnGaQ4 (Q = S, Se). These compounds are synthesized using high-temperature solid-state synthesis routes employing polychalcogenide flux or by metathesis reactions. The crystal structure of these compounds is built up of a three-dimensional (3-D) network of corner-shared supertetrahedral (T2) units, where two such 3-D networks are interlocked. The d-block metal and the main group metal, Ga, occupy the same crystallographic site with a 1:1 ratio, making it a rare form of building unit. Band structure calculations show that both the compounds are wide band gap semiconductors with band gaps of 2.25 and 1.61 eV, respectively, for Na3ZnGaS4 (I) and Na3ZnGaSe4 (II), which are slightly underestimated compared to experimentally determined band gaps of 3.0 and 1.90 eV, respectively. I and II possess ionic conductivities of 3.74 x 10-4 and 0.12 mS/cm with activation energies of 0.42 and 0.38 eV, respectively, at 30 °C. Interestingly, I shows a significantly high ionic conductivity of 0.13 mS/cm at 30 °C upon exposure to air, which could be due to water adsorption on the surface or occlusion in the grain boundaries. Assuming the vacancy-Assisted diffusion mechanism for ionic conductance, this difference is consistent with the difference on vacancy formation energies in these compounds, as predicted by DFT calculations. The bond valence sum map indicates that in both structures, the lowest energy diffusion path is one dimensional and it is along the c axis of the unit cell.

Department(s)

Physics

Second Department

Chemistry

Comments

The authors are grateful for the funding of this work by National Science Foundation (NSF) Grant DMR-1809128.

Keywords and Phrases

Interlocked Lattice; Ionic Conductivity; Sodium Superionic Conductor; Solid Electrolyte; Vacancy Formation Energy

International Standard Serial Number (ISSN)

2574-0962

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2021 American Chemical Society (ACS), All rights reserved.

Publication Date

23 Aug 2021

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