▎ 摘　　要

Silicon/carbon (Si/C) composite shows great potential to replace graphite as lithium-ion battery (LIB) anode owing to its high theoretical capacity. Exploring low-cost scalable approach for synthesizing Si/C composites with excellent electrochemical performance is critical for practical application of Si/C anodes. In this study, we rationally applied a scalable in situ approach to produce Si-carbon nanotube (Si-CNT) composite via acid etching of commercial inexpensive micro-sized Al-Si alloy powder and CNT mixture. In the Si-CNT composite, similar to 10 nm Si particles were uniformly deposited on the CNT surface. After combining with graphene sheets, a flexible self standing Si-CNT/graphene paper was fabricated with three-dimensional (3D) sandwich-like structure. The in situ presence of CNT during acid-etching process shows remarkable two advantages: providing deposition sites for Si atoms to restrain agglomeration of Si nanoparticles after Al removal from Al-Si alloy powder, increasing the cross-layer conductivity of the paper anode to provide excellent conductive contact sites for each Si nanoparticles. When used as binder-free anode for LIBs without any further treatment, in situ addition of CNT especially plays important role to improve the initial electrochemical activity of Si nanoparticles synthesized from low-cost Al-Si alloy powder, thus resulting in about twice higher capacity than Si/G paper anode. The self-standing Si-CNT/graphene paper anode exhibited a high specific capacity of 1100 mAh g(-1) even after 100 cycles at 200 mA g-1 current density with a Coulombic efficiency of >99%. It also showed remarkable rate capability improvement compared to Si/G paper without CNT. The present work demonstrates a low-cost scalable in situ approach from commercial micro-sized Al-Si alloy powder for Si-based composites with specific nanostructure. The Si-CNT/graphene paper is a promising anode candidate with high capacity and cycling stability for LIBs, especially for the flexible batteries application.