Over 50% of an engine’s energy dissipates via the exhaust and cooling systems, leading to considerable energy loss. Effectively harnessing the waste heat generated by the engine is a critical avenue for enhancing energy efficiency. Traditional exhaust heat recovery systems are limited to real-time recovery of exhaust heat primarily for engine warm-up and fail to fully optimize exhaust heat utilization. This paper introduces a novel exhaust heat recovery system leveraging thermal battery technology, which utilizes phase change materials for both heat storage and reutilization. This innovation significantly minimizes the engine’s cold start duration and provides necessary heating for the cabin during start-up. Dynamic models and thermal management system models were constructed. Parameter optimization and calculations for essential components were conducted, and the fidelity of the simulation model was confirmed through experiments conducted under idle warm-up conditions. Four distinct operational modes for engine warm-up are proposed, and strategies for transitioning between these heating modes are established. A simulation analysis was performed across four varying operational scenarios: WLTC, NEDC, 40 km/h, and 80 km/h. The results indicated that the thermal battery-based exhaust heat recovery system notably reduces warm-up time and fuel consumption. In comparison to the cold start mode, the constant speed condition at 40 km/h showcased the most significant reduction in warm-up time, achieving an impressive 22.52% saving; the highest cumulative fuel consumption reduction was observed at a constant speed of 80 km/h, totaling 24.7%. This study offers theoretical foundations for further exploration of thermal management systems in new energy vehicles that incorporate heat storage and reutilization strategies utilizing thermal batteries.