Lithiated Organic Coverages on SiO x Anodes: Promoting Li 2 O Formation and Suppressing Lithium Silicate Growth for Stable Lithium‐Ion Batteries

Silicon oxide (SiO x ) is a high‐capacity anode material for lithium‐ion batteries. SiO x offers lower irreversible capacity loss, improved cycling stability, and reduced volume expansion, which facilitate practical electrode design and manufacturing. Nevertheless, SiO x faces challenges such as the formation of inactive lithium silicates, the need for conductive carbon composites, and a relatively high lithiation potential plateau. Prelithiation has proven particularly effective, as it mitigates irreversible reactions associated with solid electrolyte interphase (SEI) formation and lithium intercalation. In this study, two lithiated organic coatings (LiOCs) were developed and applied onto the SiO x surface for long‐term stability. The LiOCs introduce additional Li + species and functional groups containing O and N atoms, which strongly interact with the surface SiOSi bonds of SiO x . This interaction redistributes the local electron density, resulting in partial electron withdrawal from oxygen atoms and alters the structural distortion of the local asymmetry of the SiOSi as well as promotes the formation of extended Si clusters prior to electrochemical cycling. The LiOCs effectively suppress the formation of lithium silicates (Li x SiO y ) while promoting Li 2 O generation. Consequently, the LiOCs@SiO x anode exhibits significantly improved cycle retention, attributed to the minimized formation of small Si clusters and enhanced interfacial Li + transport. Li 2 O offers superior Li + diffusivity compared to Li x SiO y . Combining with direct contact prelithiation from Li metal during conventional prelithiation, the LiOC‐modified SiO x anode demonstrates twin synergistic effects with Ni‐rich cathodes.