Electrochemical characteristics of nanostructured silicon anodes for lithium-ion batteries

High-aspect periodic structures with thin vertical walls are studied as regards their applicability as negative electrodes of lithium-ion batteries. The nanostructures are fabricated from single-crystal silicon using photolithography, electrochemical anodization, and subsequent anisotropic shaping. The capacity per unit of the visible surface area of the electrode and the specific internal surface area are compared for structures of varied architecture: 1D (wires), 2D (zigzag walls), and 3D structures (walls forming a grid). Main attention is given to testing the endurance of anodes based on zigzag and grid structures, performed by galvanostatic cycling in half-cells with a lithium counter electrode. The influence exerted by the geometric parameters of the structures and by the testing mode on the degradation rate is determined. It is shown that the limiting factor of the lithiation and delithiation processes is diffusion. The endurance of an electrode dramatically increases when the charging capacity is limited to $\sim$1000 mA h/g. In this case, nanostructures with 300-nm-thick walls, which underwent cyclic testing at a rate of 0.36C, retain a constant discharge capacity and a Coulomb efficiency close to 100% for more than 1000 cycles.