Interpenetrated Lattices of Quaternary Chalcogenides Displaying Magnetic Frustration, High Na-Ion Conductivity, and Cation Redox in Na-Ion Batteries

Authors

• Kartik C. Ghosh, Missouri State UniversityFollow
• Santhoshkumar Sundaramoorthy, Missouri University of Science and Technology
• Srikanth Balijapelly, Missouri University of Science and Technology
• Sudip Mohapatra, Missouri University of Science and Technology
• Sutapa Bhattacharya, Missouri University of Science and Technology
• Amitava Choudhury, Missouri University of Science and Technology

Abstract

A series of quaternary selenides, NaxMGaSe4 (M = Mn, Fe, and mixed Zn/Fe), have been synthesized for the first time employing a high-temperature solid-state synthesis route through stochiometric or polychalcogenide flux reactions. Along with the selenides, a previously reported sulfide analogue, NaxFeGaS4, is also revisited with new findings. These compounds form an interpenetrated structure made up of a supertetrahedral unit. The electrochemical evaluations exhibit a reversible (de)intercalation of ?0.6 and ?0.45 Na-ions, respectively, from Na2.87FeGaS4 (1a) and Na2.5FeGaSe4 (2) involving Fe²⁺/Fe³⁺ redox when cycled between 1.5 and 2.5 V. Mössbauer spectroscopy of 1a shows the existence of a mixed oxidation state of Fe^2+/3+ in the pristine compound and reversible oxidation of Fe²⁺ to Fe³⁺ during the electrochemical cycles. Na2.79Zn0.6Fe0.4GaSe4 possesses a reasonably high room temperature ionic conductivity of 0.077 ms/cm with an activation energy of 0.30 eV. The preliminary magnetic measurements show a bifurcation of FC-ZFC at 4.5 and 2.5 K, respectively, for 1a and Na3MnGaSe4 (4) arising most likely from a spin-glass like transition. The high negative values of the Weiss constants ?368.15 and ?308.43 K for 1a and 4, respectively, indicate strong antiferromagnetic interactions between the magnetic ions and also emphasize the presence of a high degree of magnetic frustration in these compounds.

Department(s)

Physics, Astronomy, and Materials Science

Document Type

Article

DOI

10.1021/acs.inorgchem.4c00927

Publication Date

6-24-2024

Recommended Citation

Ghosh, Kartik C.; Sundaramoorthy, Santhoshkumar; Balijapelly, Srikanth; Mohapatra, Sudip; Bhattacharya, Sutapa; and Choudhury, Amitava, "Interpenetrated Lattices of Quaternary Chalcogenides Displaying Magnetic Frustration, High Na-Ion Conductivity, and Cation Redox in Na-Ion Batteries" (2024). Faculty Scholarship. 352.
https://bearworks.missouristate.edu/articles00/352

Journal Title

Inorganic Chemistry