Failure mechanisms associated with silicon-based anodes are limiting the implementation of high-capacity lithium-ion batteries. Understanding the aging mechanism that deteriorates the anode performance and introducing novel-architectured composites offer new possibilities for improving the functionality of the electrodes. Here, the characterization of nano-architectured composite anode composed of active amorphous silicon domains (a-Si, 20 nm) and crystalline iron disilicide (c-FeSi2 , 5-15 nm) alloyed particles dispersed in a graphite matrix is reported. This unique hierarchical architecture yields long-term mechanical, structural, and cycling stability. Using advanced electron microscopy techniques, the nanoscale morphology and chemical evolution of the active particles upon lithiation/delithiation are investigated. Due to the volumetric variations of Si during lithiation/delithiation, the morphology of the a-Si/c-FeSi2 alloy evolves from a core-shell to a tree-branch type structure, wherein the continuous network of the active a-Si remains intact yielding capacity retention of 70% after 700 cycles. The root cause of electrode polarization, initial capacity fading, and electrode swelling is discussed and has profound implications for the development of stable lithium-ion batteries.
Keywords: Li-ion batteries; active alloys; composite anodes; hierarchical structures; lithium trapping.
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