Humidity-Induced Degradation of Lithium-Stabilized Sodium-Beta Alumina Solid Electrolytes

Sodium-beta alumina is a solid-state electrolyte with outstanding chemical, electrochemical, and mechanical properties. Sodium polyaluminate is successfully employed in established Na–S and Na–NiCl2 cell systems. It is a promising candidate for all-solid-state sodium batteries. However, humidity affects the performance of this solid electrolyte. In this work, the effect of humidity on disk-shaped samples of Li-stabilized sodium-beta alumina stored in three different environments is quantified. We used impedance analysis and additional characterizations to investigate the consequences of the occurring degradation, namely ion exchange and subsequent buildup of surface layers. Sodium-beta alumina’s ionic conductivity gradually deteriorates up to two orders of magnitude. This is due to layers developed superficially during storage, while its fracture strength of 240 MPa remains unaffected. Changes in microstructure, composition, and cycle life of Na|BASE|Na cells highlight the importance of proper storage conditions: In just one week of improper storage, the critical current density collapsed from the maximum of 9.1 mA cm−2, one of the highest values reported for sodium-beta alumina, to 1.7 mA cm−2 at 25 °C. The results validate former observations regarding sodium-beta alumina’s moisture sensitivity and suggest how to handle sodium-beta alumina used in electrochemical cell systems.