The Thermal Stability of Molten Lithium–Sodium–Potassium Carbonate and the Influence of Additives on the Melting Point

Abstract

The thermal stability of a molten LiNaK carbonate salt, potentially suitable for thermal energy storage, was studied up to a temperature of 1000 °C. The salt investigated was the eutectic Li2CO3–Na2CO3–K2CO3 in the proportions 32.1–33.4–34.5 wt. % and the study was done by simultaneous differential scanning calorimetry (DSC)/thermogravimetric–mass spectrometric (TG–MS) analysis in gas atmospheres of argon, air, and CO2. It was found that (i) under a blanket gas atmosphere of CO2 the LiNaK carbonate salt is stable up to at least 1000 °C. (ii) In an inert atmosphere of argon, the salt evolves gaseous CO2 soon after melting and begins to decompose at between 710 °C and 715 °C with acceleration in the CO2 evolution rate from the melt. An increase in the rate of weight loss is also observed after 707 °C. (iii) Under a blanket atmosphere of air, the gaseous CO2 evolution from the salt is observed to commence at 530 °C, the onset of decomposition detected by DSC analysis at 601 °C and the rapid rate of weight loss determined by TG analysis at 673 °C. The melting point of the LiNaK carbonate studied was between 400 °C and 405 °C. Thermodynamic modeling with Multi-Phase-Equilibrium (MPE) software developed in CSIRO Process Science and Engineering indicated that additives such as NaNO3, KCl, and NaOH lower the melting point of the LiNaK carbonate eutectic, and this was experimentally verified.