Due to their high energy density and power potential, 21700 lithium-ion battery cells are a widely used technology in hybrid and electric vehicles. Efficient thermal management is essential for maximizing the performance and capacity of Li-ion cells in both low- and high-temperature operating conditions. Optimizing thermal management systems remains critical, particularly for long-range and weight-sensitive applications. In these contexts, passive heat dissipation emerges as an ideal solution, offering effective thermal regulation with minimal additional system weight. This study aims to deepen the understanding of passive heat dissipation in 21700 battery cells and optimize their performance. Special emphasis is placed on analyzing heat transfer and the relative contributions of convective and radiative mechanisms under varying temperature and discharge conditions. Laboratory experiments were conducted under controlled environmental conditions at various discharge rates, ranging from 0.5×C to 5×C. A 3D-printed polymer casing was applied to the cell to enhance thermal dissipation, designed specifically to increase radiative heat transfer while minimizing system weight and reliance on active cooling solutions. Additionally, a numerical model was developed and optimized using experimental data. This model simulates convective and radiative heat transfer mechanisms with minimal computational demand. The optimized numerical model is intended to facilitate further investigation of the cell envelope strategy at the module and battery pack levels in future studies.