Anchoring Unimolecular Metal Chloride as a Sterically Active Site for Conformal Zinc Electrodeposition

Abstract

Abstract Aqueous zinc ion batteries are promising candidates for next‐generation energy storage systems. However, the practical application of zinc metal anodes is hindered by the challenge of uncontrollable zinc‐dendrite growth. Herein, axial‐coordinated manganese single atoms, anchored by N, Cl co‐coordinating on self‐standing carbon nanofibers, are designed to guide uniform Zn deposition. The MnCl 2 N 4 octahedral sites act as effective nucleation centers, significantly reducing the Zn adsorption energy of the carbon matrix, achieving a nucleation overpotential of 17 mV. The strong interaction between Zn and MnCl 2 N 4 sites stabilizes the initially adsorbed Zn 2+ through John‐Teller distortions, which in turn promotes subsequent zinc adsorption. In symmetric cells, the Mn‐modified carbon nanofiber electrodes exhibit excellent cycling stability with a lifespan of 200 h under a high current density of 20 mA cm −2 . Moreover, a full cell coupling a MnO 2 cathode with a Mn‐doped carbon nanofiber anode delivers outstanding cycling performance over 1400 cycles at 1 A g −1 . This work highlights the potential of axially coordinated single‐atom metals in regulating zinc deposition, offering a pathway toward durable and high‐performance ZIBs.