Conversion of Co Nanoparticles to CoS in Metal-Organic Framework-Derived Porous Carbon during Cycling Facilitates Na₂S Reactivity in a Na-S Battery

Roomerature sodium-sulfur batteries have attracted wide interest due to their high energy density and high natural abundance. Polysulfide dissolution and irreversible Na2S conversion are challenges to achieving high battery performance. Herein, we utilize a metal-organic framework-derived Co-containing nitrogen-doped porous carbon (CoNC) as a catalytic sulfur cathode host. A concentrated sodium electrolyte based on sodium bis(fluorosulfonyl)imide, dimethoxyethane, and bis(2,2,2-trifluoroethyl) ether is used to mitigate polysulfide dissolution. We tune the amount of Co present in the CoNC carbon host by acid washing. Significant improvement in reversible sulfur conversion and capacity retention is observed with a higher Co content in CoNC, with 600 mAh g-1 and 77% capacity retention for CoNC and 261 mAh g-1 and 56% capacity retention for acid-washed CoNC at cycle 50 at 80 mAh g-1. Post-mortem X-ray photoelectron spectroscopy, transmission electron microscopy, and selected area electron diffraction suggest that CoS is formed during cycling in place of Co nanoparticles and CoN4 sites. Raman spectroscopy suggests that CoS exhibits a catalytic effect on the oxidation of Na2S. Our findings provide insights into understanding the role Co-based catalysts play in sulfur batteries.