Covalently Bonded Si–Polymer Nanocomposites Enabled by Mechanochemical Synthesis as Durable Anode Materials

Silicon is one of the most promising anode materials for lithium-ion batteries due to its high theoretical capacity and low cost. However, significant capacity fading caused by severe structural degradation during cycling limits its practical implication. To overcome this barrier, we design a covalently bonded nanocomposite of silicon and poly­(vinyl alcohol) (Si–PVA) by high-energy ball-milling of a mixture of micron-sized Si and PVA. The obtained Si nanoparticles are wrapped by resilient PVA coatings that covalently bond to the Si particles. In such nanostructures, the soft PVA coatings can accommodate the volume change of the Si particles during repeated lithiation and delithiation. Simultaneously, as formed covalent bonds enhance the mechanical strength of the coatings. Due to the significantly improved structural stability, the Si–PVA composite delivers a lifespan of 100 cycles with a high capacity of 1526 mAh g^–1. In addition, a high initial Coulombic efficiency of over 86% and an average value of 99.2% in subsequent cycles can be achieved. This reactive ball-milling strategy provides a low-cost and scalable route to fabricate high-performance anode materials.