To optimize the utilization of solar energy in the latent heat thermal energy storage (LHTES) system, this study conducts exergy analysis on a paraffin-solar water shell and tube unit established in the literature to evaluate the effects of different inclination angles, inlet temperatures, original temperatures, and fluid flow rates on the exergy and exergy efficiency. Firstly, the thermodynamic characteristics of the water and the natural convection effects of the paraffin change with different inclination angles. When the inclination angle of the heat storage tank is less than 30°, the maximum exergy inlet rate rises from 0 to 144.6 W in a very short time, but it decreases to 65.7 W for an inclination angle of 60°. When the inclination angle is increased from 0° to 30°, the exergy efficiency rises from 86% to 89.7%, but it decreases from 94% to 89.9% with the inclination angle from 60° to 90°. Secondly, under the condition that the inclination angle of the energy storage unit is 60°, although increasing the inlet temperature of the solar water enhances the exergy inlet and storage and reduces the charging time, it increases the heat transfer temperature difference and the irreversible loss of the system, thus reducing the exergy efficiency. As the inlet water temperature is increased from 83 to 98 °C, the exergy efficiency decreases from 94.7% to 93.6%. Moreover, increasing the original temperature of the LHTES unit not only reduces the exergy inlet and storage rates but also decreases the available work capacity and exergy efficiency. Finally, increasing the inlet water flow rate increases the exergy inlet and storage rates slightly. The exergy efficiency decreases from 95.6% to 93.3% as the unit original temperature is increased from 15 to 30 °C, and it is enhanced from 94% to 94.6% as the inlet flow rate is increased from 0.085 to 0.34 kg/s with the unit inclination angle of 60°. It is found that arranging the shell and tube unit at an inclination angle is useful for improving the LHTES system’s thermal performance, and the exergy analysis conducted aims to reduce available energy dissipation and exergy loss in the thermal storage system. This study provides instructions for solar energy utilization and energy storage.
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