Hierarchical Porous Carbon Nanofibers with Tunable Geometries and Porous Structures Fabricated by a Scalable Electrospinning Technique

Porous carbon nanofibers (PCNFs) have rich channels for transporting ions, molecules, and nanoparticles, but the control over their porous structures is a challenge. Here, we report a scalable electrospinning technique by using poly­(tetrafluoroethylene) as a pore template, boric acid as a cross-linking agent, and polyvinyl alcohol and polyurethane as dual carbon precursors to fabricate flexible PCNFs with tunable geometries and macro/meso/microporous structures. In the water solvent, the negatively charged template cross-links with the positively charged carbon precursors to form a stable sol for electrospinning. By varying the mass ratios of these precursors, the electrospun hybrid nanofibers are directly transformed into B–F–N–O doped PCNFs with tunable macro-, meso-, and micropores after carbonization. The porosity of an individual PCNF is as high as ∼85%, and the pore volume can be tuned from 0.23 to 0.58 cm³·g^–1. When constructing high-sulfur-content (86 wt %) electrodes with the freestanding PCNF films, the porous structures with rich electroactive sites provide rapid pathways for poly-anions and have strong chemisorption of poly-sulfides, leading to a great electrochemical performance. The reported strategy offers a new perspective for synthesizing hierarchical PCNFs with appealing applications.