Controllable Synthesis and Growth Mechanism of Cracked Cowpea-Like NCNT Encapsulated with Fe3N Nanoparticles for High-Performance Anode Material in Lithium-Ion Batteries

Abstract

Fe3N nanocrystals embedded in cracked N-doped carbon nanotubes (Fe3N@NCNT) with a cowpea-like shape are innovatively prepared by metal-catalyzed graphitization and nitridization processes based on melamine and FeC2O4 precursor. The new in-situ synthesis strategy is proved to be effective to open the NCNT using a migratory metal carbide nanocatalyst via expansion effect and fabricate a metal nitride embedded NCNT with fully active ingredients. The detailed tip-growth mechanism of cracked NCNT with latitudinal-longitudinal graphene layers is studied by in-situ XRD analysis of the phase evolution of melamine and FeC2O4, and ex-situ SEM/TEM investigation of the topography correlation of NCNT and Fe3C floating catalyst. The Fe3N@NCNT microclews based anodes have a moderate carbon content of 35.45 wt%, electroactive NCNT conductive network, abundant microcracks and an open short-cavity system, showing a stable discharge capacity of 667 mAh g−1 at 0.1C, outstanding rate capability of 448 mAh g−1 at 5C and remarkable long-term cycling stability of 546 mAh g−1 after 600 cycles at 1C. The combined good electronic/ionic conductivity of cracked NCNT and robust mechanical stability of geometrically confined Fe3N nanoparticles contribute to the excellent redox activities, stabilized solid-electrolyte-interphase film and cycling durability of Fe3N@NCNT.