The fluorination method strongly influences the physical properties of the resulting fluorinated carbon materials. Two fluorination ways, direct fluorination under pure fluorine gas and controlled fluorination by the decomposition of TbF4, have been used for the fluorination of particular nanocarbons: carbon nanofibers and a mixture of carbon nanodiscs and nanocones. Then, fluorocarbon matrix structures have been determined owing to solid state 19F NMR for MAS conditions at a spinning speed of 30 kHz. It reveals that the fluorination mechanism depends on the fluorination conditions but not on the starting nanocarbons morphology, i.e. tubular or planar. Finally, the electrochemical properties of carbon nanofibers fluorinated by the two ways are detailed. Controlled fluorination allows an increase of the power densities of fluorinated carbon nanofibers used as electrode in primary lithium batteries.