Regulating the Solvation Structure of Li(+) Enables Chemical Prelithiation of Silicon-Based Anodes Toward High-Energy Lithium-Ion Batteries

The solvation structure of Li(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency (ICE) and poor cycle performance of silicon-based materials. Nevertheless, the chemical prelithiation agent is difficult to dope active Li(+) in silicon-based anodes because of their low working voltage and sluggish Li(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized SiO/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential (E(1/2)), and the prelithiation efficiency is determined by the specific influencing factors (E(1/2), Li(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-023-01068-8.