In order to solve the problem of which the dynamic response of a supercapacitor (SC) is limited due to the mismatch dynamic characteristics between the DC/DC converter and supercapacitor in an energy storage system, this paper proposes a hybrid model predictive control strategy based on a dual active bridge (DAB). The hybrid model predictive control model considers the supercapacitor and DAB in a unified way, including the equivalent series resistance and capacitance parameters of the SC. The method can obtain a large charging and discharging current of the SC, thereby not only improving the overall response speed of the system, but also expanding the actual capacity utilization range of the SC. The simulation results show that compared with the model prediction method of the dual active bridge converter, the proposed control method can effectively improve the overall response speed of the system, which can be improved by at least 0.4 ms. In addition, the proposed method increases the actual upper limit of the SC voltage, reduces the actual lower limit of the SC voltage, and then expands the actual capacity utilization range of the SC by 18.63%. The proposed method has good application prospects in improving the dynamic response performance of energy storage systems.