The　exceptional　energy　density　and　stability　of　fluorinated　carbon　(CFx)　cathode　materials　have　shone　brightly　in　the　field　of　Li　primary　batteries.　However,　the　development　of　Li/CFx　secondary　batteries　has　hit　a　bottleneck　due　to　the　high　dissociation　energy　and　band　gap　energy　of　LiF.　Herein,　a　fluorinated　biomass　hard　carbon　(FTS/Ni),　with　Ni　functional　layer　rich　in　catalytic　active　sites　deposited　on　CFx　surface　via　magnetron　sputtering,　is　synthesized,　showing　high　reversibility　of　lithium　ions　storage.　FTS/Ni　cathode　with　1.5　wt%　Ni　content　exhibits　high　capacity　of　250　mAh　g-1　within　voltage　window　of　1.5-5.0　V.　Density　functional　theory　(DFT)　calculations　confirm　that　Ni　catalyst　could　reduce　the　dissociation　energy　of　LiF,　accelerating　the　conversion　kinetics　of　LiF,　thereby　enhancing　the　secondary　electrochemical　performance　of　Li/CFx　batteries.　This　work　demonstrates　that　the　reversibility　of　LiF　within　the　voltage　window　of　1.5-5.0　V　can　be　achieved　through　Ni　catalytic　action,　pointing　out　a　promising　direction　for　the　secondary　rechargeability　of　Li/CFx　batteries.