The thermal runaway of Lithium-ion batteries (LIBs) is a fire hazard. The Accelerating Rate Calorimetry (ARC) device is commonly used to investigate thermal runaway parameters of LIBs by assuming adiabatic conditions. However, this assumption ignores internal heat transfer within the cell and external heat transfer at the cell surface. In this work, we conducted ARC experiments using prismatic LiCoO2 cells of 50 mm in side to study the effect of heat transfer limitations. Results show that the external temperature difference between this cell surface and ARC walls varies between 0 and 1.5 ℃ before thermal runaway and increases from 10 to 130 ℃ while thermal runaway occurs. Ignoring external heat transfer causes the heat of reaction of the cell to be underestimated by 12%. To study the internal heat transfer, two models are developed and show that heat transfer causes an internal temperature difference that causes an error of kinetics estimation, and the error grows with cell size. Ignoring heat transfer leads to errors on the thermal runaway parameters quantified by ARC, and these errors could propagate to battery safety design and predictions. This study contributes to designing better ARC experiments and a better understanding of battery safety.