Beyond Isolated Active Sites: Adjacent Single‐Atom‐Nanoparticle Electronic Coupling Enables Lateral Lithium Growth

ABSTRACT Precise host regulation remains pivotal for dendrite‐free lithium metal anodes (LMAs). While maximizing isolated single‐atom sites improves initial Li nucleation, their uniform adsorption energetics inherently confine Li to these initial sites, favoring localized vertical accumulation over lateral growth. Here we propose an adjacent single‐atom‐nanoparticle electronic coupling strategy to break this thermodynamic bottleneck. Via coordination‐mediated laser direct writing, we construct a hierarchical porous graphene host comprising ultrafine Co nanoparticles and adjacent Co single atoms. Precursor preorganization and the ultrafast, non‐equilibrium kinetics of laser processing concurrently drive in situ graphitization and Co‐species reconstruction, effectively suppressing the aggregation in conventional thermal synthesis. Mechanistically, rather than relying on isolated thermodynamic traps, interfacial electronic coupling reconstructs the local d ‐band center and establishes a directed spatial Li adsorption‐energy gradient. This thermodynamic driving force compels Li to sequentially occupy neighboring sites, effectively precluding localized vertical accumulation. Owing to this spatially regulated deposition, the high‐loading Li||LiFePO 4 full cells retain 71.4% capacity after 1000 cycles at 2 C. This adjacent electronic coupling strategy transcends the isolated active sites paradigm, opening a new dimension for interfacial electronic‐structure regulation in practical LMAs.