In-silico design of metal-ion batteries: Unleashing the potential of conductive polymer functionalized boron nitride nanosheets

Metal-ion batteries are considered among the most promising energy storage technologies owing to their remarkable energy density, efficiency, and cycle stability compared to other types of rechargeable systems. The development of cost-effective, high-voltage, and thermally stable hybrid materials for improved anodic performance can be accelerated by using first-principles calculations. In this study, density functional theory (DFT) simulations were employed to investigate how functionalizing two-dimensional hexagonal boron nitride nanosheets (BNNS) with conducting polymers, specifically poly-para-phenylene (PPPh), can enhance their structural, electronic, and electrochemical properties. A number of electron-withdrawing and electron-releasing substituents were also explored to understand their impact on p-electron delocalization across the polymer's backbone. The functionalization of the boron nitride sheet with the nitro-substituted PPPh resulted in a 63% reduction in the HOMO-LUMO energy gap and a significant cell voltage enhancement, with calculated voltages reaching 3.7 V for Li-, 3.2 V for Na-, 3.1 V for Be, and 6.9 V for Mg-ion batteries. Theoretical specific capacities of 244 and 217 mAh/g were predicted for the investigated LIBs and SIBs, respectively. The functionalized systems maintain a stable structural integrity, competitive thermal stability, and notable ion diffusion characteristics, confirming their potential for high-voltage, durable anode applications. • DFT modeling reveals structure-property relations in PPPh functionalized boron nitride sheets. • Electron-withdrawing/donating substituents tune band gap and charge transport characteristics. • Nitro-substituted PPPh shows 63% HOMO–LUMO energy reduction compared to pristine sheet. • Functionalized boron nitride sheets exhibit high thermal stability and improved ion mobility.