A Uniform Self‐Reinforced Organic/Inorganic Hybrid SEI Chelation Strategy on Microscale Silicon Surfaces for Stable‐Cycling Anodes in Lithium‐Ion Batteries

A promising anode material for Li-ion batteries, silicon (Si) suffers from volume expansion-induced pulverization and solid electrolyte interface (SEI) instability. Microscale Si with high tap density and high initial Coulombic efficiency (ICE) has become a more anticipated choice, but it will exacerbate the above issues. In this work, the polymer polyhedral oligomeric silsesquioxane-lithium bis (allylmalonato) borate (PSLB) is constructed by in situ chelation on microscale Si surfaces via click chemistry. This polymerized nanolayer has an "organic/inorganic hybrid flexible cross-linking" structure that can accommodate the volume change of Si. Under the stable framework formed by PSLB, a large number of oxide anions on the chain segment preferentially adsorb LiPF₆ and further induce the integration of inorganic-rich, dense SEI, which improves the mechanical stability of SEI and provides accelerated kinetics for Li⁺ transfer. Therefore, the Si4@PSLB anode exhibits significantly enhanced long-cycle performance. After 300 cycles at 1 A g^-1 , it can still provide a specific capacity of 1083 mAh g^-1 . Cathode-coupled with LiNi_0.9 Co_0.05 Mn_0.05 O₂ (NCM90) in the full cell retains 80.8% of its capacity after 150 cycles at 0.5 C.