Surface SiO₂ Thickness Controls Uniform-to-Localized Transition in Lithiation of Silicon Anodes for Lithium-Ion...

Silicon is a promising anode material for lithium-ion batteries because of its high capacity, but its widespread adoption has been hampered by a low cycle life arising from mechanical failure and the absence of a stable solid-electrolyte interphase (SEI). Understanding SEI formation and its impact on cycle life is made more complex by the oxidation of silicon materials in air or during synthesis, which leads to SiO coatings of varying thicknesses that form the true surface of the electrode. In this paper, the lithiation of SiO₂-coated Si is studied in a controlled manner using SiO₂ coatings of different thicknesses grown on Si wafers via thermal oxidation. SiO₂ thickness has a profound effect on lithiation: below 2 nm, SEI formation followed by uniform lithiation occurs at positive voltages versus Li/Li⁺. Si lithiation is reversible, and SiO₂ lithiation is largely irreversible. Above 2 nm SiO₂, voltammetric currents decrease exponentially with SiO₂ thickness. For 2-3 nm SiO₂, SEI formation above 0.1 V is suppressed, but a hold at low or negative voltages can initiate charge transfer whereupon SEI formation and uniform lithiation occur. Cycling of Si anodes with an SiO₂ coating thinner than 3 nm occurs at high Coulombic efficiency (CE). If an SiO₂ coating is thicker than 3-4 nm, the behavior is totally different: lithiation at positive voltages is strongly inhibited, and lithiation occurs at poor CE and is highly localized at pinholes which grow over time. As they grow, lithiation becomes more facile and the CE increases. Pinhole growth is proposed to occur via rapid transport of Li along the SiO₂/Si interface radially outward from an existing pinhole, followed by the lithiation of SiO₂ from the interface outward.