Origin of Outstanding Phase and Moisture Stability in a Na3P1-xAsxS4 Superionic Conductor

Shun Li Shang, Zhaoxin Yu, Yi Wang, Donghai Wang, Zi Kui Liu

Research output: Contribution to journalArticlepeer-review

48 Scopus citations


Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na3P1-xAsxS4 (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na3P1-xAsxS4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H2O) stability of Na3P1-xAsxS4 by shifting the reaction products from the easy-forming oxysulfides (such as Na3POS3 and Na3PO2S2 with H2S release) to the difficult-forming hydrates (such as Na3P1-xAsxS4·nH2O with n = 8 and/or 9) due mainly to a weaker As-O affinity compared to that of P-O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionic conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na3P0.62As0.38S4) but also an excellent chemical stability with respect to temperature, composition, and moisture.

Original languageEnglish (US)
Pages (from-to)16261-16269
Number of pages9
JournalACS Applied Materials and Interfaces
Issue number19
StatePublished - May 17 2017

All Science Journal Classification (ASJC) codes

  • General Materials Science


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