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

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 Na 3 P 1– x As x S 4 (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 Na 3 P 1– x As x S 4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H 2 O) stability of Na 3 P 1– x As x S 4 by shifting the reaction products from the easy-forming oxysulfides (such as Na 3 POS 3 and Na 3 PO 2 S 2 with H 2 S release) to the difficult-forming hydrates (such as Na 3 P 1– x As x S 4 · n H 2 O 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 Na 3 P 0.62 As 0.38 S 4 ) but also an excellent chemical stability with respect to temperature, composition, and moisture.