Home-made fluorinated mesocarbon microbeads (F-MCMBs) were synthesised and employed in sodium batteries. Flexible, binder-free F-MCMB film electrodes were fabricated to enhance the cycle stability, and 65 cycles were achieved, which is the longest lifespan reported thus far. Nitrogen-doped graphene nanosheets (N-GNS) were also introduced as a catalyst, with the aim of lowering the voltage gap.