Lithium Redistribution Mechanism within Silicon-Graphite Electrodes: Multi-Method Approach and Method Validation

Li redistribution processes within Si-graphite composite (SiG) electrodes are analyzed using in situ and operando X-ray diffraction (XRD), ex situ light microscopy (LM), in situ optical microscopy of cross-sectioned full cells (CS-IOM), and 3D microstructure-resolved simulations of full cells. First, the lithiation behavior of graphite and SiG full cells (Si content 20.8 wt.-%) is analyzed. The results are used as validation of the methods (XRD, LM, CS-IOM, simulation). Second, the Li redistribution between the graphite component and Si component within SiG electrodes is investigated: By operando XRD measurements during charging in comparison with relaxed cells, a higher lithiation degree in the graphite component is found during charging compared to the relaxed state, indicating Li redistribution from graphite to Si during relaxation. The Li redistribution is directly observed by in situ and ex situ optical microscopy, where the golden LiC 6 phase disappears during a 24 h relaxation period. The results are supported by simulations showing the variation in the Li concentration, not only in graphite but also within the Si component. Furthermore, all methods find that the Li redistribution is more pronounced at a higher C-rate of 0.5 C, suggesting a preference for graphite lithiation over Si lithiation.