Semi-Immobilized Molecular Electrocatalysts for High-Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries constitute promising next-generation energy storage devices due to the ultrahigh theoretical energy density of 2600 Wh kg–1. However, the multiphase sulfur redox reactions with sophisticated homogeneous and heterogeneous electrochemical processes are sluggish in kinetics, thus requiring targeted and high-efficient electrocatalysts. Herein, a semi-immobilized molecular electrocatalyst is designed to tailor the characters of the sulfur redox reactions in working Li–S batteries. Specifically, porphyrin active sites are covalently grafted onto conductive and flexible polypyrrole linkers on graphene current collectors. The electrocatalyst with the semi-immobilized active sites exhibits homogeneous and heterogeneous functions simultaneously, performing enhanced redox kinetics and a regulated phase transition mode. The efficiency of the semi-immobilizing strategy is further verified in practical Li–S batteries that realize superior rate performances and long lifespan as well as a 343 Wh kg–1 high-energy-density Li–S pouch cell. This contribution not only proposes an efficient semi-immobilizing electrocatalyst design strategy to promote the Li–S battery performances but also inspires electrocatalyst development facing analogous multiphase electrochemical energy processes.