ALD TiO2 coated silicon nanowires for lithium ion battery anodes with enhanced cycling stability and coulombic efficiency

Abstract

We demonstrate that silicon nanowire (SiNW) Li-ion battery anodes that are conformally coated with TiO₂ using atomic layer deposition (ALD) show a remarkable performance improvement. The coulombic efficiency is increased to ∼99%, among the highest ever reported for SiNWs, as compared to 95% for the baseline uncoated samples. The capacity retention after 100 cycles for the nanocomposite is twice as high as that of the baseline at 0.1 C (60% vs. 30%), and more than three times higher at 5 C (34% vs. 10%). We also demonstrate that the microstructure of the coatings is critically important for achieving this effect. Titanium dioxide coatings with an as-deposited anatase structure are nowhere near as effective as amorphous ones, the latter proving much more resistant to delamination from the SiNW core. We use TEM to demonstrate that upon lithiation the amorphous coating develops a highly dispersed nanostructure comprised of crystalline LiTiO₂ and a secondary amorphous phase. Electron energy loss spectroscopy (EELS) combined with bulk and surface analytical techniques are employed to highlight the passivating effect of TiO₂, which results in significantly fewer cycling-induced electrolyte decomposition products as compared to the bare nanowires.