Electrochemical lithiation of silicon with varied crystallographic orientation

The anisotropy of lithium intercalation into the silicon anodes of Li-ion batteries is studied on microstructures having the form of a grid with 0.5-$\mu$m-thick vertical walls and on silicon wafers of varied orientation. Electrochemical lithiation is performed at room temperature in the galvanostatic mode. The charging curves of the microstructure and flat Si anodes are examined. Secondary-ion mass spectroscopy is used to determine the distribution of intercalated Li atoms across the wafer thickness. The experimental data are analyzed in terms of the two-phase model in which the lithiation process is limited by the propagation velocity of the front between the amorphous alloy with a high Li content and the crystalline Si substrate. The relationship between the rates of Li intercalation into different crystallographic planes: (110), (111), and (100), is found to be $V_{110}:V_{111}:V_{100}$ = 3.1: 1.1: 1.0. It is demonstrated that microstructure anodes with (110) walls have the highest cycle life and withstand 600 cycles when charged and discharged at a rate of 0.36 C.