Structural and Electrochemical Investigation during the First Charging Cycles of Silicon Microwire Array Anodes for High Capacity Lithium Ion Batteries

Silicon microwire arrays embedded in Cu present exceptional performance as anode material in Li ion batteries. The processes occurring during the first charging cycles of batteries with this anode are essential for good performance. This paper sheds light on the electrochemical and structural properties of the anodes during the first charging cycles. Scanning Electron Microscopy, X-ray diffractommetry, and fast Fourier transformation impedance spectroscopy are used for the characterization. It was found that crystalline phases with high Li content are obtained after the first lithiation cycle, while for the second lithiation just crystalline phases with less Li are observable, indicating that the lithiated wires become amorphous upon cycling. The formation of a solid electrolyte interface of around 250 nm during the first lithiation cycle is evidenced, and is considered a necessary component for the good cycling performance of the wires. Analog to voltammetric techniques, impedance spectroscopy is confirmed as a powerful tool to identify the formation of the different Si-Li phases.