Laser‐Induced High‐Density Bi–F–C Sites to Unleash Potent Li⁺ Adsorption for Stable Lithium Anodes

Abstract

Abstract The synthesis of high‐loading single‐atom materials remains a significant challenge due to the intrinsic tendency of metal atoms to aggregate. To overcome this limitation, an electrostatic pre‐organization and laser‐driven carbonization (EPO–LDC) strategy is developed. Nafion sulfonates electrostatically pre‐organize Bi 3+ at the molecular scale, while ultrafast laser quenching enables non‐equilibrium synthesis, initiating simultaneous carbon reconstruction and fluorine‐mediated covalent bonding within nanoseconds. This rapid thermal confinement kinetically restricts atomic diffusion, thereby circumventing the aggregation pathways inherent to conventional thermal processes. Concurrently, fluorine ligands offer thermodynamic stabilization through strong Bi─F bonds and optimize charge redistribution via electronegativity‐driven orbital hybridization. This dual stabilization achieves a high‐density (9.63 wt.%) atomic dispersion of bismuth within a fluorinated porous carbon network (Bi@CF) without aggregation. Theoretical calculations reveal that Bi–F–C sites exhibit an exceptional Li adsorption energy of −9.82 eV, far exceeding those of conventional lithiophilic anodes (−1–−5 eV). The combination of atomic‐scale lithiophilicity and laser‐induced hierarchical porosity enables multiscale ion regulation, resulting in remarkable electrochemical stability. The EPO–LDC strategy thus provides a scalable industrial pathway for producing high‐loading single‐atom architectures with precisely tailored coordination environments.