•Novel fin structures are proposed for heat transfer enhancement of PCM.•Visualization of the melting process of PCM within the BTMS is presented.•Thermal management performance of PCM-Fin based BTMS is evaluated. Phase change materials (PCM) based battery thermal management system (BTMS) usually suffers from the low thermal conductivity of PCM. In this paper, novel fin structures which consist of longitudinal fins and cylindrical rings are proposed for heat transfer enhancement. Experiments are firstly designed to compare the thermal performance of different BTMSs. Results demonstrate that the PCM-Fin system shows superior performance over the pure battery system and the PCM system. Numerical simulations are also conducted based on the model validation with the experimental data to reveal the underlying mechanisms. It is found that fin structures not only increase the heat transfer area but also introduce a thermal conductive network within the PCM, which contributes positively to the improvement of thermal performance of the battery. Moreover, the effects of the position of rings, the number of rings and fins, and the heat generation rate on the thermal management performance are evaluated. Results show that the optimal numbers for rings and fins are 1 and 8, respectively, and the recommended dimensionless distance between ring and battery is 0.2. It is also found that the PCM-Fin system can control the temperature rise of the battery even under the heat generation rate of 20 W.