摘要：Owing to the excellent redox reversibility and structural diversity,polytriphenylamine(PTPAn)has been regarded as one of the promising cathode candidates for sodium-ion ***,it still suffers from the bulk aggregation and low operating capacity in practical *** by the in-situ polymerization,leaf-like PTPAn nanosheets are uniformly introduced on the surface of carbon nanofibers(CNFs)to form the free-standing CNF@PTPAn composite ***,the formation mechanism of the leaf-on-branch structure of CNF@PTPAn composites is systematically explored,confirming that the controlling of oxidation rate and growth degree plays crucial roles in tuning the morphology and active material content of the composite *** by the capacity-cutting analysis,the effective coupling between the active PTPAn and conductive CNFs can provide fast electron/ion-shuttling channels and deepen the electrochemical reaction *** 50mAg^(-1),the capacity of the optimized CNF@PTPAn composite can reach 105mAh g^(-1),with a stable rate capability of 78mAh g^(-1)even at 400mAg^(-1)after 500 cycles in a half *** detailed kinetic analysis confirms that the ion-storage behaviors in the lowvoltage region can be tailored for the improved capacitive contribution and diffusion ***,the flexible CNF-based full cell with CNF@PTPAn as the cathode and CNFs as the anode exhibits a high energy density of 60Wh kg^(-1)at 938Wkg^(-1).Based on this,the rational design is expected to provide more possibilities to obtain advanced freestanding electrode systems.