Lithiation of Silicon Nanoparticles Confined in Carbon Nanotubes

Silicon has the highest theoretical lithium storage capacity of all materials at 4200 mAh/g; therefore, it is considered to be a promising candidate as the anode of high-energy-density lithium-ion batteries (LIBs). However, serious volume changes caused by lithium insertion/deinsertion lead to a rapid decay of the performance of the Si anode. Here, a Si nanoparticle (NP)-filled carbon nanotube (CNT) material was prepared by chemical vapor deposition, and a nanobattery was constructed inside a transmission electron microscope (TEM) using the Si NP-filled CNT as working electrode to directly investigate the structural change of the Si NPs and the confinement effect of the CNT during the lithiation and delithiation processes. It is found that the volume expansion (∼180%) of the lithiated Si NPs is restricted by the wall of the CNTs and that the CNT can accommodate this volume expansion without breaking its tubular structure. The Si NP-filled CNTs showed a high reversible lithium storage capacity and desirable high rate capability, because the pulverization and exfoliation of the Si NPs confined in CNTs were efficiently prevented. Our results demonstrate that filling CNTs with high-capacity active materials is a feasible way to make high-performance LIB electrode materials, taking advantage of the unique confinement effect and good electrical conductivity of the CNTs.