Enhanced d‐p Orbital Hybridization for Lithium Polysulfide Capturing and Lithium Deposition Inducing of AgVO₃ Skeleton Enabling High‐Performance Li‐Sulfur Batteries

Abstract The dendrite growth and volume expansion of the Li metal anode, as well as the LiPSs “shuttle effect” and slow conversion kinetics of the S cathode, have severely hampered the large‐scale development of LSBs. Herein, a simple hydrothermal method is employed to synthesize rod‐like AgVO 3 , which is then used as the Li metal anode current collector and the separator modification, respectively. As the Li metal anode current collector, AgVO 3 has a strong Li affinity, which can lower Li nucleation overpotential and guide uniform deposition of Li metal. The AgVO 3 ‐modified separator can accelerate the redox kinetics of LiPSs and achieve the anchoring of LiPSs. The results of DFT calculation and experiments reveal that the AgVO 3 enable the Ag horizontal d orbitals (d xy /d x 2 ‐y 2 ) to hybridize with the S p orbital to form additional σ/σ* and π/π*. The activation of horizontal d orbitals can increase LiPSs anchoring ability, reduce the reaction barrier, and accelerate LiPSs transformation. Hence, the LSBs assembled with the Li@AgVO 3 anode and AgVO 3 modified separator show excellent cycle performance. This work gives a novel idea for the application of high catalytic performance materials represented by AgVO 3 , and its unique catalytic performance can successfully achieve LSBs with high performance.