Work

Electronic‐Structure Engineering Coordinates Na Nucleation Thermodynamics and Deposition Kinetics for Stable Sodium Metal Batteries

Year: 2026

Type: article

Abstract: ABSTRACT Sodium metal batteries are limited by uncontrolled Na nucleation and nonuniform deposition, which originate from insufficient interfacial sodiophilicity and heterogeneous ion/electric‐field transport. Herein, we design a flexible lotus‐root‐like hierarchical porous carbon nanofiber framework embedded with ultrafine vanadium nitride (VN) nanoparticles (VN@HPCNF) is developed to synchronously coordinate these two processes through synergistic electronic‐structure and structural engineering. Density functional theory calculations reveal that the electronic structure of VN creates intrinsically sodiophilic sites, where electron‐rich N atoms initiate Na adsorption and V centers stabilize Na through Na‐3s/V‐3d orbital hybridization, thereby lowering the nucleation barrier. Meanwhile, COMSOL simulations reveal that the interconnected porous architecture simultaneously homogenizes the electric‐field distribution and Na + flux, alleviates localized current‐density accumulation, and guides confined and homogeneous Na deposition. The synergistic regulation of atomic‐scale electronic interactions and structural‐scale ion/electric‐field transport enables dendrite‐free Na growth. Consequently, VN@HPCNF exhibits stable cycling over 1000 h at 2 mA cm −2 , a low plating/stripping overpotential of ≈16 mV, and a high Coulombic efficiency (CE) of 99.86% at 4 mA cm −2 . This work identifies electronic‐structure‐induced sodiophilicity as a decisive descriptor for regulating Na deposition, providing a mechanistic design principle for stable alkali‐metal anodes.

Source: Small

DOI: 10.1002/smll.76108