Three-Dimensional Porous Si and SiO2 with In Situ Decorated Carbon Nanotubes As Anode Materials for Li-ion Batteries.

A high-capacity Si anode is always accompanied by very large volume expansion and structural collapse during the lithium-ion insertion/extraction process. To stabilize the structure of the Si anode, magnesium vapor thermal reduction has been used to synthesize porous Si and SiO2 (pSS) particles, followed by in situ growth of carbon nanotubes (CNTs) in pSS pores through a chemical vapor deposition (CVD) process. Field-emission scanning electron microscopy and high-resolution transmission electron microscopy have shown that the final product (pSS/CNTs) possesses adequate void space intertwined by uniformly distributed CNTs and inactive silica in particle form. pSS/CNTs with such an elaborate structural design deliver improved electrochemical performance, with better coulombic efficiency (70% at the first cycle), cycling capability (1200 mAh g-1 at 0.5 A g-1 after 200 cycles), and rate capability (1984, 1654, 1385, 1072, and 800 mAh g-1 at current densities of 0.1, 0.2, 0.5, 1, and 2 A g-1, respectively), compared to pSS and porous Si/CNTs. These merits of pSS/CNTs are attributed to the capability of void space to absorb the volume changes and that of the silica to confine the excessive lithiation expansion of the Si anode. In addition, CNTs have interwound the particles, leading to significant enhancement of electronic conductivity before and after Si-anode pulverization. This simple and scalable strategy makes it easy to expand the application to manufacturing other alloy anode materials.