Templated and Catalytic Fabrication of N-Doped Hierarchical Porous Carbon–Carbon Nanotube Hybrids as Host for Lithium–Sulfur Batteries

Nitrogen-doped hierarchical porous carbon and carbon nanotube hybrids (N-HPC-CNTs) are fabricated by simple pyrolysis of the N-rich raw material melamine-formaldehyde (MF) resin in the presence of nano-CaCO3 and a bimetallic combination of Fe-Co catalyst. During carbonization, nano-CaCO3 acts as a template for creating a hierarchical porous carbon, and the N atoms originated from MF resin are in situ doped into the carbon matrix simultaneously. Meanwhile, volatile gases generated by the thermal decomposition of MF resin could serve as carbon and nitrogen sources to grow nitrogen-doped CNTs on HPC. The growth mechanism is the same as that for conventional chemical vapor deposition (CVD) growth of CNTs on the metal catalysts, but the technological requirements are obviously not as harsh as those for the CVD method. Low-cost raw materials and simple equipment are sufficient for the growth. Moreover, the density and length of the CNTs are tunable, which can be simply adjusted via applying different amounts of Fe-Co catalysts. Such an N-doped hybrid structured carbon with mesopores can not only effectively prompt the physical and chemical adsorption of polysulfides but also ensures a fast electron transfer because of the incorporation of CNTs, which provides sufficient conducting pathways and effective connections between the CNTs and HPC. Furthermore, CNTs grown on HPC can act as physical barriers to block the large pores on HPC, thereby reducing the polysulfide loss. Benefiting from the advantages, the N-HPC-CNT hybrids are a desirable host prospect for Li-S batteries.