Hollow carbon nanofibers with dynamic adjustable pore sizes and closed ends as hosts for high-rate lithium-sulfur battery cathodes

Abstract

Designing a better carbon framework is critical for harnessing the high theoretical capacity of Li-S batteries and avoiding their drawbacks, such as the insulating nature of sulfur, active material loss, and the polysulfide shuttle reaction. Here, we report an ingenious design of hollow carbon nanofibers with closed ends and protogenetic mesopores in the shell that can be retracted to micropores after sulfur infusion. Such dynamic adjustable pore sizes ensure a high sulfur loading, and more importantly, eliminate excessive contact of sulfur species with the electrolyte. Together, the high aspect ratio and thin carbon shells of the carbon nanofibers facilitate rapid transport of Li⁺ ions and electrons, and the closed-end structure of the carbon nanofibers further blocks polysulfide dissolution from both ends, which is remarkably different from that for carbon nanotubes with open ends. The obtained sulfur-carbon cathodes exhibit excellent performance marked by high sulfur utilization, superior rate capability (1,170, 1,050, and 860 mA·h·g⁻¹ at 1.0, 2.0, and 4.0 C (1 C = 1.675 A·g⁻¹), respectively), and a stable reversible capacity of 847 mA·h·g⁻¹ after 300 cycles at a high rate of 2.0 C.