In situ growth of surface-reconstructed aluminum fluoride nanoparticles on N, F codoped hierarchical porous carbon nanofibers as efficient ORR/OER bifunctional electrocatalysts for rechargeable zinc-air batteries

Modified porous carbon fibers have emerged as crucial electrocatalytic materials for zinc-air battery (ZAB) systems. However, most methods for preparing porous carbon fibers are complex and exhibit single functionality and poor catalytic activity, which hinders the development of ZABs. In this study, we design and synthesize a novel type of N, F codoped hierarchical porous carbon fiber with in situ growth of aluminum fluoride nanoparticles (AlF₃@HPCNFs) through electrospinning and high-temperature carbonization. The N, F codoping effectively adjusts the charge density of neighboring carbon atoms and introduces additional active sites. Furthermore, the catalytic process induces surface reconstruction of AlF₃ nanoparticles, allowing for their full exposure to the liquid electrolyte and accelerated catalytic reactions. Additionally, this interconnected hierarchical porous structure accelerates mass transfer at the oxygen/carbon-based substrate/electrolyte three-phase interfaces, thereby enhancing reaction kinetics and the accessibility of catalytic active sites, ultimately improving the utilization efficiency of these sites. Consequently, the AlF₃@HPCNFs catalyst exhibits excellent bifunctional performance with a narrow potential difference (△E = 0.67 V). Moreover, the obtained bifunctional electrocatalyst is utilized for rechargeable ZABs, surpassing commercially available Pt/C + RuO₂ cells in terms of high specific capacity (796 mAh g_zn^-1) and outstanding cycling stability (over 500 h). This research demonstrates the potential of AlF₃@HPCNFs as a bifunctional electrocatalyst and introduces a simplified and effective method for the fabrication of metal fluoride-modified and hierarchically porous carbon nanofibers for rechargeable ZABs.