To reduce the thermal runaway risk of lithium-ion batteries, a good thermal management system is critically required. As phase change materials can absorb a lot of heat without the need for extra equipment, they are employed in the thermal management of batteries. The thermal management of a Sanyo 26,650 battery was studied in this work by using different composite phase change materials (CPCMs) at different charge–discharge rates. The thorough analysis on the thermal conductivity of CPCMs and the effect of CPCMs was conducted on the maximum surface temperature while charging and discharging. The findings demonstrate the ability of the composite thermal conductivity filler to increase thermal conductivity. It is increased to 1.307 W/(m K) as the ratio of silica and graphene is 1:1 (CPCM-3). The CPCMs can reduce the surface temperature of the cell, and the cooling effect of CPCM-3 is the most obvious, which can reduce the maximum temperature of the cell surface by 13.7 °C and 19 °C under 2 C and 3 C conditions. It is also found that the risk of thermal runaway of batteries under CPCMs thermal management is effectively reduced, ensuring the safe operation of the battery. This research can assist in the safe application of batteries and the development of new energy sources.