A High‐Volumetric‐Capacity Cathode Based on Interconnected Close‐Packed N‐Doped Porous Carbon Nanospheres for Long‐Life Lithium–Sulfur Batteries

Abstract This study reports a Li–S battery cathode of high volumetric capacity enabled by novel micro‐ and mesostructuring. The cathode is based on monodisperse highly porous carbon nanospheres derived from a facile template‐ and surfactant‐free method. At the mesoscale, the nanospheres structure into interconnected close‐packed clusters of a few microns in extent, thus facilitating the fabrication of dense crack‐free high areal sulfur loading (5 mg cm⁻²) cathodes with high electrical conductivity and low cathode impedance. A combination of the nitrogen doping (5 wt%), high porosity (2.3 cm³ g⁻¹), and surface area (2900 m² g⁻¹) at the microscale enables high sulfur immobilization and utilization. The cathode delivers among the best reported volumetric capacity to date, above typical Li‐ion areal capacity at 0.2 C over 200 cycles and low capacity fading of 0.1% per cycle at 0.5 C over 500 cycles. The compact cathode structure also ensures a low electrolyte requirement (6 µL mg⁻¹), which aids a low overall cell weight, and further, among the best gravimetric capacities published to date as well.