Amine- and Amide-Functionalized Mesoporous Carbons: A Strategy for Improving Sulfur/Host Interactions in Li–S Batteries

Lithium–sulfur (Li–S) batteries are of great interest due to their potentially high energy density, but the low electronic conductivity of both the sulfur (S8) cathode active material and the final discharge product lithium sulfide (Li2S) require the use of a conductive host. Usually made of relatively hydrophobic carbon, such hosts are typically ill-suited to retain polar discharge products such as the intermediate lithium polysulfides (LiPs) and the final Li2S. Herein, we propose a route to increase the sulfur utilization by functionalizing the surface of ordered mesoporous carbon CMK3 with polar groups. These derivatized CMK3 materials are made using a simple two-step procedure of bromomethylation and subsequent nucleophilic substitution with amine or amide nucleophiles. We demonstrate that, compared to the unfunctionalized control, these modified CMK3 surfaces have considerably larger binding energies with LiPs and Li2S, which are proposed to aid the electrochemical conversion between S8 and Li2S by keeping the LiPs species in close proximity to the carbon surface during Li–S battery cycling. As a result, the functionalized cathodes exhibit significantly improved specific capacities relative to their unmodified precursor.