This research investigates the dynamic behavior and impact of various factors on the hydraulic, thermal, and exergetic characteristics of a solar-based thermoelectric device using a pin–fin heatsink cooled by supercritical CO2. A comprehensive numerical model analyzes the heat dissipation and performance of the power generator, integrating a thermoelectric generator and a pin–fin heatsink with various pin shapes. Key geometric and operational parameters, such as the height of PN (P-type and N-type semiconductor) legs of the TEG, the number of thermocouples, operating pressure, Reynolds number, and CO2 temperature, are examined for a comprehensive performance assessment. The study highlights the superior performance of CO2 coolant over traditional water-cooling system. Near the critical temperature of CO2, enhanced heat transfer significantly boosts power output, conversion efficiency, and exergetic efficiency. For example, at 8 MPa, the TEG’s (thermoelectric generator) power output increases from 1.31 mW at 295 K to 2.35 mW at 310 K. Comparisons reveal that while water coolant lowers the cold side temperature more effectively, it results in reduced power output due to decreased temperature differentials and increased pressure loss. Conversely, CO2 coolant maintains higher cold side temperatures while having advantages in power output. At 315 K, the cold side temperature with water is 315.7 K compared to 346.7 K with CO2. Increasing the number of thermocouples from 18 to 32 for a leg height of 1 mm leads to an approximate 102.3 % increase in voltage. Raising the PN leg height from 1 mm to 2 mm for an NTC of 50 results in a nearly 99.8 % increase in voltage. Lozenge-shaped fin produces a peak power output of 2.73 mW, while square fin generates 2.62 mW. This research underscores CO2’s potential as a high-performance coolant in solar thermoelectric applications, offering insights into optimizing system design for maximum efficiency.
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