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Abstract
Lithium–sulfur batteries (LSBs) have tremendous attractive interest for their high theoretical energy density, natural abundance, and environmental friendliness. However, the commercialization remains constrained by the shuttle effect and sluggish kinetics of polysulfides. Herein, a spraying/discharging strategy is employed to fabricate binder‐free ω‐Li
3
V
2
O
5
(ω‐LVO) catalytic network with multi‐polarization centers by intercalating Li‐ions into tetrahedral V
2
O
5
for addressing the mentioned issues. Li (0.51 eV) and V (0.57 eV), which have a strong positive electric potential, and O (−0.57 eV), which has a strong negative electric potential, exhibit high polarity that can capture polysulfides effectively. In addition, the amounts of the polarity sites would be significantly increased because the catalyst is composed of light elements. Therefore, the ω‐LVO octahedron can catalyze polysulfides to short‐chains sufficiently. The blue shift in synchronous ultraviolet‐visible spectra and ultra‐low Tafel plots of 34 and 20 mV dec
−1
at two discharge plateaus demonstrate excellent kinetics behavior even with a low catalyst loading. Furthermore, the conductive networks facilitate electronic/ionic transmission and thereby boost their electrochemical performances. This work offers an efficacious method to promote kinetics behaviors and lessen the gap between theoretical specific capacities and future commercialization of LSBs.