Impact of Catholyte Lewis Acidity at the Molten Salt-NaSICON Interface in Low-Temperature Molten Sodium Batteries

Low-temperature molten sodium batteries comprising molten sodium anodes, a NaSICON solid-state separator, and molten halide salt catholytes offer promise as low-cost, earth-abundant energy storage technologies. The emergence of a specific, high-voltage, sodium iodide (NaI)-based catholyte chemistry has prompted the evaluation of chemical and electrochemical properties of the molten salts, particularly at critical interfaces with high-performance NaSICON separators. Herein, batteries operated at 110 degrees C with NaI-AlCl3-based catholytes of differing Lewis acidities were evaluated. Batteries with >50 mol % AlCl3 (acidic catholytes) experienced a linear decline in energy efficiency during cycling, whereas batteries with >50 mol % NaI (basic catholytes) maintained >95% energy efficiency for 50 cycles (>80 days) at 2.5 mA cm(-2). A three-electrode cell was developed, enabling identification of the NaSICON-catholyte interface as the source of increased battery impedance. Complementary physical and chemical characterization of the NaSICON exposed to acidic and basic catholytes showed no changes in crystallinity, bulk morphology, or bulk chemical composition, but surface sensitive X-ray photoelectron spectroscopy (XPS), however, revealed subtle changes in local NaSICON surface chemistry. In addition, Raman spectroscopy indicated that stably performing basic catholytes lack the dimer species Al2Cl6I- present in acidic catholytes. Select thermodynamic and formal charge assessments suggest that preferential interactions between these acidic dimeric species and the NaSICON surface may be responsible for the observed increases in electrochemical impedance and degraded battery performance. These results indicate that maintaining a Lewis basic catholyte avoids such potentially deleterious interactions, enabling efficient and stable battery cycling.