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Overall, co-doping with high-valent cations led to improved afterglow duration."Zero-strain" insertion materials are essential for high-performance Li-ion batteries, but the experimental determination of changes in their local structures remains challenging. In this study, we successfully visualized the reaction scheme of a perfect zero-strain material, (Li0.75Zn0.25)[Li0.417Ti1.583]O4 with a spinel framework, using operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The operando XRD/XAS technique, which provided