Mechanistic Understanding of Metal Phosphide Host for Sulfur Cathode in High-Energy-Density Lithium–Sulfur Batteries

For solving the drawbacks of low conductivity and the shuttle effect in a sulfur cathode, various nonpolar carbon and polar metal compounds with strong chemical absorption ability are applied as sulfur host materials for lithium–sulfur (Li–S) batteries. Nevertheless, previous research simply attributed the performance improvement of sulfur cathodes to the chemical adsorption ability of polar metal compounds toward lithium polysulfides (LPS), while a deep understanding of the enhanced electrochemical performance in these various sulfur hosts, especially at the molecular levels, is still unclear. Herein, for a mechanistic understanding of superior metal phosphide host in Li–S battery chemistry, an integrated phosphide-based host of CF/FeP@C (carbon cloth with grown FeP@C nanotube arrays) is chosen as the model, and this binder-free cathode can exclude interference from the binder and conductive additives. With a systematic electrochemical investigation of the loading sulfur in such oxide- and phosphide-based hosts (CF/Fe3O4@C and CF/FeP@C), it is found that CF/FeP@C@S shows much superior Li–S performances. The greatly enhanced performance of CF/FeP@C@S suggests that FeP can well suppress the shuttle effect of LPS and accelerate their transformation during the charge–discharge process. The first-principles calculations reveal the performance variations of Fe3O4 and FeP in Li–S batteries mainly because the shifts of the p band of the FeP could accelerate the interfacial electronics transfer dynamics by increasing the electronic concentration in the Fermi level of adsorbed Li2S4. The current work sheds light on the promising design of superior Li–S batteries from both theoretical and experimental aspects.