In situ transmission electron microscopy observation of pulverization of aluminum nanowires and evolution of the thin surface Al_2O_3 layers during lithiation-delithiation cycles

摘要

Lithiation-delithiation cycles of individual aluminum nanowires (NWs) with naturally oxidized Al_2O_3 surface layers (thickness 4-5 nm) were conducted in situ in a transmission electron microscope. Surprisingly, the lithiation was always initiated from the surface Al_2O_3 layer, forming a stable Li-Al-O glass tube with a thickness of about 6-10 nm wrapping around the NW core. After lithiation of the surface Al _2O_3 layer, lithiation of the inner Al core took place, which converted the single crystal Al to a polycrystalline LiAl alloy, with a volume expansion of about 100%. The Li-Al-O glass tube survived the 100% volume expansion, by enlarging through elastic and plastic deformation, acting as a solid electrolyte with exceptional mechanical robustness and ion conduction. Voids were formed in the Al NWs during the initial delithiation step and grew continuously with each subsequent delithiation, leading to pulverization of the Al NWs to isolated nanoparticles confined inside the Li-Al-O tube. There was a corresponding loss of capacity with each delithiation step when arrays of NWs were galvonostatically cycled. The results provide important insight into the degradation mechanism of lithium-alloy electrodes and into recent reports about the performance improvement of lithium ion batteries by atomic layer deposition of Al_2O_3 onto the active materials or electrodes.