Synergistic Prelithiation and In Situ Nitrogen Doping via Li3N in SiO Anodes: A Dual‐Benefit Pathway to Achieving Enhanced Li+ Kinetics and High Initial Coulombic Efficiency

Abstract Silicon monoxide (SiO) has garnered significant attention as a promising anode material for high‐energy‐density lithium‐ion batteries due to its lower volume expansion relative to pure silicon (Si) and its higher capacity compared to graphite. Nevertheless, the poor intrinsic electronic/ionic conductivity and the low initial Coulombic efficiency (ICE) of SiO result in inferior rate capability and inadequate practical energy density, hindering its commercial viability. Here, a simultaneous prelithiation and in situ nitrogen (N) doping approach for SiO utilizing lithium nitride (Li 3 N), which significantly enhances both the ICE and lithium‐ion (Li + ) diffusion kinetics, is proposed. N atoms are not only incorporated into the carbon layer on the surface of SiO but also form a uniformly distributed amorphous Li 2 SiN 2 phase within the SiO, facilitating Li + transport. Molecular dynamics simulations demonstrate that the Li + diffusion coefficient of amorphous Li 2 SiN 2 is significantly higher than that of other crystalline phases present in the prelithiated SiO matrix. The 1.5 Ah pouch cells further validate that the SiON‐0.175/graphite||NCM811 exhibits a high ICE of 88.06%, and it retains 51.5% of its capacity even under 4C fast charging conditions. This study offers new insights into the development of next‐generation SiO anode materials with high ICE and high‐rate performance.