Developing polyoxometalate‐cyclodextrin cluster‐organic supramolecular framework (POM‐CD‐COSF) still remains challenging due to an extremely difficult task in rationally interconnecting two dissimilar building blocks. Here we report an unprecedented POM‐CD‐COSF crystalline structure produced through the self‐assembly process of a Krebs‐type POM, [Zn2(WO2)2(SbW9O33)2]10−, and two β‐CD units. The as‐prepared POM‐CD‐COSF‐based battery separator can be applied as a lightweight barrier (approximately 0.3 mg cm−2) to mitigate the polysulfide shuttle effect in lithium‐sulfur batteries. The designed Li−S batteries equipped with the POM‐CD‐COSF modified separator exhibit remarkable electrochemical performance, attributed to fast Li+ diffusion through the supramolecular channel of β‐CD, efficient polysulfide‐capture ability by the dynamic host–guest interaction of β‐CD, and improved sulfur redox kinetics by the bidirectional catalysis of POM cluster. This research provides a broad perspective for the development of multifunctional supramolecular POM frameworks and their applications in Li−S batteries.

No abstract

A novel supramolecular assembly built from Keggin-type polyoxometalates and [18]crown-6 ether building blocks was first applied as sulfur host in lithium–sulfur batteries to resolve remaining critical challenge of polysulfide shuttle effect.

Al–S battery (ASB) is a promising energy storage device, notable for its safety, crustal abundance, and high theoretical energy density. However, its development faces challenges due to slow reaction kinetics and poor reversibility. The creation of a multifunctional cathode material that can both adsorb polysulfides and accelerate their conversion is key to advancing ASB. Herein, a composite composed of polyoxometalate nanohybridization‐derived Mo2C and N‐doped carbon nanotube‐interwoven polyhedrons (Co/Mo2C@NCNHP) is proposed for the first time as an electrochemical catalyst in the sulfur cathode. This composite improves the utilization and conductivity of sulfur within the cathode. DFT calculations and experimental results indicate that Co enables the chemisorption of polysulfides while Mo2C catalyzes the reduction reaction of long‐chain polysulfides. X‐ray photoelectron spectroscopy (XPS) and in situ UV analysis reveal the different intermediates of Al polysulfide species in Co/Mo2C@NCNHP during discharging/charging. As a cathode material for ASB, Co/Mo2C@NCNHP@S composite can deliver a discharge‐charge voltage hysteresis of 0.75 V with a specific capacity of 370 mAh g−1 after 200 cycles at 1A g−1.

This review outlines recent progress in aqueous zinc–sulfur batteries, highlighting electrolyte modification, additive engineering, and cathode enhancements. It also proposes future research directions to inspire solutions for overcoming challenges.