25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium‐Ion Batteries

Alloying anodes such as silicon are promising electrode materials for next‐generation high energy density lithium‐ion batteries because of their ability to reversibly incorporate a high concentration of Li atoms. However, alloying anodes usually exhibit a short cycle life due to the extreme volumetric and structural changes that occur during lithium insertion/extraction; these transformations cause mechanical fracture and exacerbate side reactions. To solve these problems, there has recently been significant attention devoted to creating silicon nanostructures that can accommodate the lithiation‐induced strain and thus exhibit high Coulombic efficiency and long cycle life. In parallel, many experiments and simulations have been conducted in an effort to understand the details of volumetric expansion, fracture, mechanical stress evolution, and structural changes in silicon nanostructures. The fundamental materials knowledge gained from these studies has provided guidance for designing optimized Si electrode structures and has also shed light on the factors that control large‐volume change solid‐state reactions. In this paper, we review various fundamental studies that have been conducted to understand structural and volumetric changes, stress evolution, mechanical properties, and fracture behavior of nanostructured Si anodes for lithium‐ion batteries and compare the reaction process of Si to other novel anode materials.