With the advancement of battery technology and the expansion of market demand, large-capacity lithium batteries are increasingly being used in electric vehicles and energy storage industries. At the same time, battery aging significantly affects the thermal characteristics of lithium batteries. However, research on the coupling of aging characteristics and thermal characteristics of large-capacity lithium batteries is very limited. This study adopts a combined experimental and simulation approach to systematically investigate the relationship between aging and thermal characteristics of large-capacity LiFePO4 batteries. Firstly, the batteries were cycled at 0.75C under different temperatures, revealing that the aging degree of large-capacity batteries increases sequentially at 10 °C, 25 °C, and 40 °C. Subsequently, the changes in internal resistance and entropy coefficient before and after battery aging were measured, leading to the conclusion that the irreversible heat increases rapidly after aging, while the reversible heat remains almost unchanged. Finally, using experimentally measured parameters, liquid cooling thermal models were established for fresh battery packs and battery packs aged under 10 °C, 25 °C, and 40 °C cycling. The simulation results indicate that after aging, the Tmax, Tave, and ΔTmax inside the battery pack increase significantly, and the aging of the battery pack reduces the effectiveness of the battery thermal management (BTM) system designed for fresh battery packs. To address this issue, it is necessary to increase the inlet flow rate of the coolant to 0.1 m/s and reduce the inlet temperature of the coolant to 21 °C to maintain the effectiveness of the BTM. This study provides important reference significance for the BTM of large-capacity lithium batteries throughout their life cycle.