Catalysis‐Derived Robust Solid Electrolyte Interphase for Stable SiO Anode

Silicon monoxide (SiO) is a next‑generation high‑capacity anode for lithium‑ion batteries, yet its commercialization is severely plagued by drastic volume expansion, unstable solid electrolyte interphase (SEI), and sluggish reaction kinetics. Herein, we report a catalytic interfacial engineering strategy by constructing Ni nanoparticle‑decorated SiO (SiO@NC‑Ni) to break through these bottlenecks. The embedded metallic Ni nanoparticles act as electrocatalytic centers that selectively promote the adsorption and reductive decomposition of fluorine‑containing electrolyte components, thereby in situ constructing a dense, mechanically robust, and LiF‑rich SEI layer in the initial cycles. This catalytically tailored SEI layer effectively suppresses persistent electrolyte degradation, accommodates large volume fluctuations, and preserves electrode integrity. Meanwhile, Ni nanoparticles coupled with N‑doped carbon coating layer build a continuous conductive network that drastically boosts electronic conductivity and Li + transport kinetics. Benefiting from these synergies, the SiO@NC‑Ni anode delivers a high initial Coulombic efficiency of 82.4%, a remarkable reversible capacity of 833.07 mAh g −1 at 0.1 A g −1 after 100 cycles, and an excellent rate capability of 421.21 mAh g −1 even at 5.0 A g −1 . This work highlights the critical role of interfacial electrocatalysis in regulating SEI chemistry and provides a universal paradigm for developing high‑performance SiO‑based anodes toward high‑performance lithium‑ion batteries.