Germanium Nanowires-in-Graphite Tubes <i>via</i> Self-Catalyzed Synergetic Confined Growth and Shell-Splitting Enhanced Li-Storage Performance

Abstract

Despite the high theoretical capacity, pure Ge has various difficulties such as significant volume expansion and electron and Li⁺ transfer problems, when applied as anode materials in lithium ion battery (LIB), for which the solution would finally rely on rational design like advanced structures and available hybrid. Here in this work, we report a one-step synthesis of Ge nanowires-in-graphite tubes (GNIGTs) with the liquid Ge/C synergetic confined growth method. The structure exhibits impressing LIB behavior in terms of both cyclic stability and rate performance. We found the semiclosed graphite shell with thickness of ∼50 layers experience an interesting splitting process that was driven by electrolyte diffusion, which occurs before the Ge–Li alloying plateau begins. Two types of different splitting mechanism addressed as “inside-out”/zipper effect and “outside-in” dominate this process, which are resulted from the SEI layer growing longitudinally along the Ge–graphite interface and the lateral diffusion of Li⁺ across the shell, respectively. The former mechanism is the predominant way driving the initial shell to split, which behaves like a zipper with SEI layer as invisible puller. After repeated Li⁺ insertion/exaction, the GNIGTs configuration is finally reconstructed by forming Ge nanowires–thin graphite strip hybrid, both of which are in close contact, resulting in enormous enchantment to the electrons/Li⁺ transport. These features make the structures perform well as anode material in LIB. We believe both the progress in 1D assembly and the structure evolution of this Ge–C composite would contribute to the design of advanced LIB anode materials