Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO2 on Si is often inevitable. However, it is not clear if this layer has a positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties of the SiO2 lithiation products and by the convolution of chemical and electrochemical effects during the anode lithiation process. In this study, LixSiOy thin films as model materials for lithiated SiO2 were deposited by magnetron sputtering at ambient temperature, with the goal of (1) decoupling chemical reactivity from electrochemical reactivity and (2) evaluating the physical and electrochemical properties of LixSiOy. X-ray photoemission spectroscopy analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO2 can be achieved through sputtering. Our density functional theory calculations also confirm that the possible phases formed by lithiating SiO2 are very close to the measured film compositions. Scanning probe microscopy measurements show that the mechanical properties of the film are strongly dependent on lithium concentration, with a ductile behavior at a higher Li content and a brittle behavior at a lower Li content. The chemical reactivity of the thin films was investigated by measuring the AC impedance evolution, suggesting that LixSiOy continuously reacts with the electrolyte, in part because of the high electronic conductivity of the film determined from solid-state impedance measurements. The electrochemical cycling data of the sputter-deposited LixSiOy/Si films also suggest that LixSiOy is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.
}, year = {2018}, journal = {ACS Applied Materials & Interfaces}, volume = {10}, pages = {38558 - 38564}, month = {10/2018}, issn = {1944-8244}, doi = {10.1021/acsami.8b10895}, language = {eng}, }