Modulating p‐Band Center of M‐N ₄ Site via Engineering Second‐Shell Carbon Defects for High‐Performance Lithium‐Carbon Composite Anodes

ABSTRACT Lithium (Li) metal anodes remain commercially constrained by irreversible losses from inherent electrochemical activity. While carbon‐based materials mitigate Li metal deterioration through regulated deposition, dendrite suppression, and volume accommodation, the fabrication of stable Li─C composite anodes is consistently hindered by the intrinsic lattice mismatch. To address this atomic‐scale incompatibility, we engineer carbon defects adjacent to single‐atom Zn‐N 4 sites with high dispersibility (denoted as ZND), altering their symmetrical electron distribution to release stronger electroactivity, using metal‐polyphenol coordination and structural rearrangement. Theoretical simulations indicate that the electronic configuration is reconstructed, and the p‐band center of the electronegative nitrogen atoms located in the first shell is significantly elevated, notably intensifying the interaction with the molecular orbitals of the reactant Li + . Experimental characterization confirms that ZND optimizes Li hetero‐nucleation behavior, promoting the formation of dense Li deposition layers and an inorganic‐rich solid electrolyte interface (SEI). The Li||ZND half‐cell achieves over 450 cycles of stable cycling at current densities of 1.0 and 2.0 mA cm −2 , respectively, with a fixed areal capacity of 1.0 mAh cm −2 . Consequently, the fabricated Li─C composite anode demonstrates exceptional stability in ether‐based electrolytes. This work establishes a paradigm for atomic‐level engineering in Li─C composite anodes.