LAUSR

Silicon (Si) is regarded as the most promising anode material for high‐energy lithium‐ion batteries (LIBs) due to its high theoretical capacity, and low working potential. However, the large volume variation during the continuous lithiation/delithiation processes easily leads to structural damage and serious side reactions. To overcome the resultant rapid specific capacity decay, the nanocrystallization and compound strategies are proposed to construct hierarchically assembled structures with different morphologies and functions, which develop novel energy storage devices at nano/micro scale. The introduction of assembly strategies in the preparation process of silicon‐based materials can integrate the advantages of both nanoscale and microstructures, which significantly enhance the comprehensive performance of the prepared silicon‐based assemblies. Unfortunately, the summary and understanding of assembly are still lacking. In this review, the understanding of assembly is deepened in terms of driving forces, methods, influencing factors and advantages. The recent research progress of silicon‐based assembled anodes and the mechanism of the functional advantages for assembled structures are reviewed from the aspects of spatial confinement, layered construction, fasciculate structure assembly, superparticles, and interconnected assembly strategies. Various feasible strategies for structural assembly and performance improvement are pointed out. Finally, the challenges and integrated improvement strategies for assembled silicon‐based anodes are summarized.