Leveraging Direct Pyrolysis for the Synthesis of 10 nm Monodispersed Fe3O4/Fe3C NPS@Carbon to Improve SupercapacitANCE in Acidic Electrolyte

Abstract

AbstractThe prevailing practice advocates pre–oxidation of electrospun Fe–salt/polymer nanofibers (Fe–salt/polymer Nf) before pyrolysis as advantageous in the production of high–performance FeOx@carbon nanofibers supercapacitors (FeOx@C). However, our study systematically challenges this notion by demonstrating that pre–oxidation facilitates the formation of polydispersed and large FeOx nanoparticles (FeOx@CI−DA) through “external” Fe3+ Kirkendall diffusion from carbon, resulting in subpar electrochemical properties. To address this, direct pyrolysis of Fe–salt/polymer Nf is proposed, promoting “internal” Fe3+ Kirkendall diffusion within carbon and providing substantial physical confinement, leading to the formation of monodispersed and small FeOx nanoparticles (FeOx@CDA). In 1 M H2SO4, FeOx@CDA demonstrates ~2.60× and 1.26× faster SO42− diffusivity, and electron transfer kinetics, respectively, compared to FeOx@CI−DA, with a correspondingly ~1.50× greater effective surface area. Consequently, FeOx@CDA exhibits a specific capacity of 161.92 mAhg−1, ~2× higher than FeOx@CI−DA, with a rate capability ~19 % greater. Moreover, FeOx@CDA retains 94 % of its capacitance after 5000 GCD cycles, delivering an energy density of 26.68 Whkg−1 in a FeOx@CDA//FeOx@CDA device, rivaling state–of–the–art FeOx/carbon electrodes in less Fe–corrosive electrolytes. However, it is worth noting that the effectiveness of direct pyrolysis is contingent upon hydrated Fe–salt. These findings reveal a straightforward approach to enhancing the supercapacitance of FeOx@C materials.