Deciphering the Impact of Current, Composition, and Potential on the Lithiation Behavior of Si‐Rich Silicon‐Graphite Anodes

Abstract Adding silicon (Si) to graphite (Gr) anodes is an effective approach for boosting the energy density of lithium‐ion batteries, but it also triggers mechanical instability due to Si volume changes upon (de)lithiation reactions. In this work, component‐specific (de)lithiation dynamics on Si‐rich (30 and 70 wt.% Si) SiGr anodes at various charge/discharge C‐rates are unveiled and compared to a graphite‐only electrode (100Gr) via operando synchrotron X‐ray diffraction coupled with differential capacity plots analysis. Results show preferential lithiation of amorphous Si above ≈200 mV and competing lithiation of Gr, amorphous Si, and crystalline Si below ≈200 mV. Discharge proceeds via sequential delithiation of Gr and amorphous lithium silicide. Si shifts the interconversion potentials of graphite intercalation compounds, lowering the Gr state of charge compared to 100Gr. In the 30% Si electrode, crystalline Si amorphization at potentials <110 mV is found to be kinetically hindered at C‐rates higher than C/5, which can be key for enhancing the cycling stability of SiGr anodes. The 70% Si electrode exhibits restricted lithium diffusion in Gr, full Si amorphization, and Li 15 Si 4 formation. These findings related to the potential‐ and current‐dependent dynamic changes on SiGr blends are crucial for designing stable high energy density SiGr anodes.