Direct Growth of Si, Ge, and Si–Ge Heterostructure Nanowires Using Electroplated Zn: An Inexpensive Seeding Technique for Li‐Ion Alloying Anodes

Abstract

A scalable and cost‐effective process is used to electroplate metallic Zn seeds on stainless steel substrates. Si and Ge nanowires (NWs) are subsequently grown by placing the electroplated substrates in the solution phase of a refluxing organic solvent at temperatures >430 °C and injecting the respective liquid precursors. The native oxide layer formed on reactive metals such as Zn can obstruct NW growth and is removed in situ by injecting the reducing agent LiBH4. The findings show that the use of Zn as a catalyst produces defect‐rich Si NWs that can be extended to the synthesis of Si–Ge axial heterostructure NWs with an atomically abrupt Si–Ge interface. As an anode material, the as grown Zn seeded Si NWs yield an initial discharge capacity of 1772 mAh g−1 and a high capacity retention of 85% after 100 cycles with the active participation of both Si and Zn during cycling. Notably, the Zn seeds actively participate in the Li‐cycling activities by incorporating into the Si NWs body via a Li‐assisted welding process, resulting in restructuring the NWs into a highly porous network structure that maintains a stable cycling performance.

Challenges and Recent Progress on Silicon‐Based Anode Materials for Next‐Generation Lithium‐Ion Batteries

“…Structure designing are the most specific and effective way to accommodate volume variation of Si anode during discharging/charging process. [ 17 ] These structured designing included the different nanostructured Si (nanoparticles, [9a,18] nanolayers, [ 19 ] nanowires, [ 20 ] nanotubes [ 21 ] ), morphological structures of Si (core–shell, [ 22 ] yolk–shell, [ 23 ] porous [ 24 ] ) and the atomic‐scale structures design of Si (doping, [ 25 ] lattice deformation, [ 26 ] heterostructure [ 27 ] ). Importantly, the three structure design strategies both combined with various flexible and rigid materials, which were clarified the promising methods for optimization of Si‐based anode for LIBs.…”

Interface engineering towardhigh‐efficiencyalloy anode for next‐generation energy storage device

“…Volume expansion is a common problem for alloy anode materials 24 . Figure 2B exhibits a schematic of a typical alloy anode particles failure mechanism 25 .…”

Subsuming the Metal Seed to Transform Binary Metal Chalcogenide Nanocrystals into Multinary Compositions

“…Subsequent supersaturation promotes NC growth where alloying of the growth phase and seed is feasible depending on the charge balance of coordination sites. There is also another less studied route to materialize multicomponent metal chalcogenide 1D nanostructures, where a liquid metal droplet is used to catalyze the desired semiconductor phase in a solution–liquid–solid (SLS) growth mechanism. , This approach has been long studied for covalent network nanowires of Si, Ge but has also been used to form metal-seeded CuInE 2 , ZnE, CdE (E = S, Se, Te) nanowires. − The seed here is a catalyst to lower the eutectic temperature and at the end of the reaction remains intact as a metal particle either coupled to the semiconductor component as a heterostructure or separated in solution. − …”