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 AgVO₃, which is then used as the Li metal anode current collector and the separator modification, respectively. As the Li metal anode current collector, AgVO₃ has a strong Li affinity, which can lower Li nucleation overpotential and guide uniform deposition of Li metal. The AgVO₃‐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 AgVO₃ enable the Ag horizontal d orbitals (d_xy/d_x²_‐y²) 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@AgVO₃ anode and AgVO₃ modified separator show excellent cycle performance. This work gives a novel idea for the application of high catalytic performance materials represented by AgVO₃, and its unique catalytic performance can successfully achieve LSBs with high performance.