Green Fabrication of Silkworm Cocoon-like Silicon-Based Composite for High-Performance Li-Ion Batteries

Designing yolk-shell nanostructures is an effective way of addressing the huge volume expansion issue for large-capacity anode and cathode materials in Li-ion batteries (LIBs). Previous studies mainly focused on adopting a SiO₂ template through HF etching to create yolk-shell nanostructures. However, HF etching is highly corrosive and may result in a significant reduction of Si content in the composite. Herein, a silkworm cocoon-like silicon-based composite is prepared through a green approach in which Al₂O₃ was selected as a sacrificial template. The void space between the outer nitrogen-doped carbon (NC) shell formed by chemical vapor deposition using a pyridine precursor and the inside porous silicon nanorods (p-Si NRs) synthesized by magnesiothermic reduction of ordered mesoporous silica nanorods can be generated by etching Al₂O₃ with diluted HCl. The obtained p-Si NRs@void@NC composite is utilized as an anode material for LIBs, which exhibits a large initial discharge capacity of 3161 mAh g^-1 at 0.5 A g^-1, excellent cycling behavior up to 300 cycles, and super rate performance. Furthermore, a deep understanding of the mechanism for the yolk-shell nanostructure during the Li-alloying process is revealed by in situ transmission electron microscopy and finite element simulation.