Realizing rapid and reversible Zn2+ storage at the cathode is imperative for the advancement of aqueous Zn-ion batteries (ZIBs), which offer an excellent option for large-scale electrochemical energy storage. However, owing to limitations of the structural stability of previously investigated frameworks, the Zn2+ storage processes remain unclear, thus hindering progress towards the above goal. Herein, we present the novel application of MoVTe oxide with an M1 phase (MVT-M1) as a potential cathode material for ZIBs. MVT-M1 features broad and robust tunnels that facilitate reversible Zn2+ insertion/extraction during cycling, as well as rich redox centers (Mo, V, and Te) to aid in charge redistribution, resulting in good performances in ZIBs. The exceptional resilience of MVT-M1 to high-energy electron beams allows for direct observation of Zn2+ insertion/extraction at the atomic scale within the tunnels for the first time using high-angle annular dark field scanning transmission electron microscopy; the storage location of zinc ions within the cathode is accurately determined layer by layer from the surface to the bulk phase by employing time-of-flight secondary ion mass spectrometry. Additionally, solvent molecules (H2O and methanol) are also found inside the tunnels along with Zn2+. Due to the broader heptagonal tunnels and Te ions in the hexagonal tunnels, MVT-M1 exhibits good cycling stability, outperforming MoVTe oxide with the M2 phase (no heptagonal tunnels) and MoV oxide with the M1 phase (no Te). These findings hold significant importance in advancing our understanding of the Zn2+ storage mechanism and enable the design of novel materials specifically optimized for efficient Zn2+ storage.
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