Laser-Synthesized Metastable Bismuth Nanocrystals Chemically Bonded to Reduced Graphene Oxide for Excellent Lithium Storage

• • Bi nanocrystals synthesized by pulsed laser irradiation (5.5 nm) undergo lattice restructuring during solvothermal reaction, shrinking to 2 nm—the smallest reported for Bi/C composites, enabling enhanced surface area and active sites for lithium storage. • • The Bi-rGO-2 anode achieves a reversible capacity of 586.7 mAh g−1 after 500 cycles at 100 mA g−1, nearly doubling the 318 mAh g−1 of Bulk Bi/rGO, demonstrating superior cycling stability and structural integrity. • • Strong Bi–O–C covalent bonds between Bi and rGO suppress particle aggregation and provide efficient ion/electron transport channels, mitigating volume expansion during alloying/dealloying, critical for long-term battery operation. • • Theoretical calculations confirm higher binding energy between Bi and rGO at smaller particle sizes, and kinetic analysis reveals accelerated Li+ diffusion, validating the design principle of metastable nanocrystal engineering for high-performance anodes.