Self-Assembled Polyoxometalate Nanodots as Bidirectional Cluster Catalysts for Polysulfide/Sulfide Redox Conversion in Lithium-Sulfur Batteries.

Polyoxometalates (POMs) are a class of discrete molecular inorganic metal-oxide clusters with reversible multielectron redox capability. Taking advantage of their redox properties, POMs are thus expected to be directly involved in the lithium-sulfur batteries (Li-S, LSBs) system as a bidirectional molecular catalyst. Herein, we design a three-dimensional porous structure of reduced graphene-carbon nanotube skeleton supported POM catalyst as a high-conductive and high-stability host material. Based on various spectroscopic techniques and in situ electrochemical studies together with computational methods, the catalytic mechanism of POM clusters in Li-S battery was systematically clarified at the molecular level. The constructed POM-based sulfur cathode delivers a reversible capacity 1110 mAh g-1 at 1.0 C and cycling stability up to 1000 cycles at 3.0 C. Furthermore, Li-S pouch/beaker batteries with a POM-based cathode were successfully demonstrated. This work provides essential inputs to promote molecular catalyst design and its application in LSBs.