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Achieving Superconformal Sodium Deposition on Carbon Nanofiber Film by Constructing Axial Oxygen Coordinated Copper Atomic Sites

Enhao Liu,Yibo Zhu,Shengyong Gao,Junping Hu,Wei Feng,Jisheng Zhou

Achieving superconformal deposition of metallic sodium on 3D matrices is a critical challenge for sodium metal batteries (SMBs). Herein, flexible 3D carbon nanofiber films anchored with axial O-coordinated CuN 4 O 2 single-atom sites (CuN 4 O 2 -CNF) by a ZnCl 2 -mediated thermal activation strategy is designed. Unlike conventional planar CuN 3 configurations obtained without ZnCl 2 , the axial O in CuN 4 O 2 sites exhibits a high density of states near the Fermi level, modulating the electronic structure of neighboring Cu and N. This lowers Na + adsorption energy, accelerates charge transfer and enhances electrolyte permeability, enabling superconformal sodium deposition. As a result, the CuN 4 O 2 -CNF achieves an ultra-low nucleation overpotential of 10 mV, a coulombic efficiency of 99.92% over 8,000 h, and exceptional cycling stability exceeding 10,000 h in symmetric cells. The full coin cells paired with a Na 3 V 2 (PO 4 ) 3 cathode retain 89.5 mA h g −1 after 1,000 cycles at 1 A g −1 and deliver 80.3 mA h g −1 at 5 A g −1 , demonstrating superior rate capability. The pouch cells also maintain a stable capacity of 75.8 mA h g −1 after 150 cycles at 58.5 mA g −1 . These results highlight the transformative potential of axial-coordination for designing high-performance metal batteries, offering insights into interfacial dynamics and host architectures for next-generation energy-storage systems.