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Nitrate molten salt is widely used as high-efficiency thermal storage material for advancing concentrated solar power (CSP) technology, which is due to their many excellent properties such as thermal stability, high energy density, low viscosity and liquefaction temperature. However, the measurements of properties for nitrates are not convenient at high temperature melting state for long time period, which can cause the corrosion of storage vessel made by stainless steel by nitrates salt, and the theoretical simulations are also faced to large challenge of complicate models and long computing period for optimizing the performance of nitrate molten salts. In this study, an empirical electron theory (EET) of solids and molecules is used to investigate the valence electron structure, cohesive energy, and melting points of MNO3 (M = Li, Na, K) and their decomposition byproducts (nitrites) systematically for revealing the mechanism of these properties. The calculated bond lengths, cohesive energy, and melting points of nitrate molten salt agree with the experimental ones. The study reveals the strongly dependence of physical properties upon the valence electron structure. The bonding strength and ability strongly depend upon the covalent electron pairs nα. The cohesive energy exhibits a positive correlation with the number of valence electrons nc. The melting mechanism is originated from the melting broken of M-O (M = Li, Na, K) bond by the vibrating of thermal phonon at melting temperature, it is suggested the atomic cluster of NO3 is still stabilized during the melting process. In binary nitrate molten-salts, the calculated liquidus lines match the measured ones in their binary phase diagrams well. The liquid temperatures show significant positive correlation with the weighted average of number of covalent electron pairs (nM-O) on M-O bond. The thermodynamic simulation models are used systematically to predict the viscosity, electrical conductivity, and thermal conductivity of the binary nitrate molten-salts. Based on calculations of EET and thermodynamic simulations, the binary nitrates molten salts are optimized with compositions of 0.5LiNO3-0.5NaNO3、0.5LiNO3-0.5KNO3 and 0.6NaNO3-0.4KNO3, which are suggested as good candidates for advanced molten salts with high thermal and electrical conductivity, low viscosity, and low liquefaction temperature.
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Keywords:
- nitrates /
- valence electron structure /
- melting point /
- cohesive energy
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