Controllable synthesis of one-dimensional silicon nanostructures based on the dual effects of electro-deoxidation and the Kirkendall effect

In this study,we successfully synthesized silicon nanotubes(Si-NTs)and silicon nanowires(Si-NWs)in a controllable manner using a catalyst-and template-free method through the direct electrolysis of SiO_(2)in a molten CaCl_(2)-CaO system,while also proposing a novel formation mechanism for Si-NTs.Si-NWs are formed through electro-deoxidation when the cell voltage is within the range of CaO decomposition voltage and SiO_(2)decomposition voltage.By subsequently adjusting the voltage to a value between the decomposition potentials of CaCl_(2)and CaO,in-situ electro-deoxidation of CaO takes place on the surface of the synthesized Si-NWs,leading to the formation of a Ca layer.The formation of Ca-Si diffusion couple leads to the creation of vacancies within the Si-NWs,as the outward diffusion rate of Si exceeds the inward diffusion rate of Ca.These differential diffusion rates between Si and Ca in a diffusion couple exhibit an analogy to the Kirkendall effect.These vacancies gradually accumulate and merge,forming large voids,which ultimately result in the formation of hollow SiCa-NTs.Through a subsequent dealloying process,the removal of the embedded calcium leads to the formation of Si-NTs.Following the application of a carbon coating,the Si-NTs@C composite showcases a high initial discharge capacity of 3211 mAh·g^(-1)at 1.5 A·g^(-1)and exhibits exceptional long-term cycling stability,maintaining a capacity of 977 mAh·g^(-1)after 2000 cycles at 3.0 A·g^(-1).