Manipulating the Conversion Kinetics of Polysulfides by Engineering Oxygen p-Band of Halloysite for Improved Li-S Batteries

Small. 2022 Feb;18(6):e2105661. doi: 10.1002/smll.202105661. Epub 2021 Dec 2.

Abstract

Polar oxides are widely used as the cathodes to impede the shuttle effect in lithium-sulfur batteries, but suffer from the sluggish desorption and conversion of polysulfides due to too strong affinity of polysulfides on oxygen sites. Herein, employing halloysite as a model, an approach to overcome these shortcomings is proposed via engineering oxygen p-band center by loading titanium dioxide nanoparticles onto Si-O surface of halloysite. Using density functional theory calculations, it is predicted that electron transfer from titanium dioxide nanoparticles to interfacial O sites results in downshift of p-band center of O sites that promote desorption of polysulfides and the cleavage of Li-S and S-S, accelerating the conversion kinetics of polysulfides. The designed composite cathode material delivers outstanding electrochemical performance in Li-S batteries, outperforming the recently reported similar cathodes. The concept could provide valuable insight into the design of other catalysts for Li-S batteries and beyond.

Keywords: Li-S batteries; electron transfer; halloysite; p-band center; polysulfides.