The Li₂SO₄-Na₂SO₄ System for Thermal Energy Storage

In this paper, the system Li₂SO₄-Na₂SO₄ is proposed as a candidate material for thermal energy storage applications at high temperatures (450-550 °C). Depending on the composition, the thermal energy can be stored by using a eutectoid reaction and solid-solid phase transition. In these types of systems, all the components (reagent and products) are in the solid state. This work includes the theoretical analysis (based on the Calphad method) of the system selected obtaining all the theoretical parameters (for example, enthalpies of reaction, transition temperatures, volume expansion, and the heat capacities) necessary to determine the theoretical performance in terms of thermal energy storage. The theoretical analysis allowed to identify two compositions (Li₂SO₄/Na₂SO₄ 79/21 and 50/50) in the phase diagram with the most promising theoretical enthalpy of transformation (270 J/g and 318 J/g, respectively) corresponding to a eutectoid reaction and a solid-solid phase transition (stoichiometric compound LiNaSO₄). The experimental analysis carried out allowed to confirm the great potential of this system for TES application even if some discrepancies with the theoretical calculation have been observed experimentally (energy densities lower than expected). For the two compositions studied, 79/21 and 50/50, the enthalpies of reaction are 185 J/g and 160 J/g, respectively. The reactivity of the system was tested under different experimental conditions preparing materials with a different degree of nanocrystallization to favor the diffusion in the solid state, testing the reactivity of the materials under controlled atmosphere and under air, and performing preliminary durability analysis (cycling behavior up to 20 cycles) to test the stability and reversibility.