Expediting Desolvation–Diffusion Kinetics by Self‐Cascade Catalysis for Durable Low‐Temperature Zinc Metal Batteries

Abstract Dendrite‐free Zn metal anodes with robust interface are highly desired for the practical application of aqueous zinc‐metal based batteries (AZMBs), while their stability is hindered by the untoward [Zn(H 2 O) 6 ] 2+ desolvation and succedent deposition with dissatisfactory kinetic barriers, especially under low‐temperature environment. Herein, a self‐cascade catalytic strategy on accelerating interfacial desolvation and optimizing diffusion is proposed by designing an atomically dispersed Bi within the deficient LaMnO 3.15 perovskite (SABi/U‐LMO) layer on Zn anode. Theoretical calculations demonstrate that the d ‐band center and nonbonding state near the Fermi level of SABi/U‐LMO alleviate the corrosion of H 2 O and accelerate the dissociation of Zn 2+ ─H 2 O bond by promoting the rapid filling of the empty 4s orbital of the Zn 2+ , as revealed by electrochemical and spectroscopic results. Meanwhile, the redistribution of electric field with SABi/U‐LMO realizes the delocalization and lateral growth of Zn atoms. Consequently, the cells with SABi/U‐LMO render an impressive lifetime up to 5000 h at 1 mA cm −2 as well as a high Coulombic efficiency of 99.59% over 2000 cycles under 0 °C. Full cell also stabilizes the capacity retention of ∼100% after 900 cycles at 1 A g −1 under −20 °C, verifying the feasibility of self‐cascade catalysis in realizing high‐performance AZMBs.