Elucidating a dissolution-deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO₂ batteries

Aqueous Zn/MnO₂ batteries with their environmental sustainability and competitive cost, are becoming a promising, safe alternative for grid-scale electrochemical energy storage. Presented as a promising design principle to deliver a higher theoretical capacity, this work offers fundamental understanding of the dissolution-deposition mechanism of Zn/β-MnO₂. A multimodal synchrotron characterization approach including three operando X-ray techniques (powder diffraction, absorption spectroscopy, and fluorescence microscopy) is coupled with elementally resolved synchrotron X-ray nano-tomography. Together they provide a direct correlation between structural evolution, reaction chemistry, and 3D morphological changes. Operando synchrotron X-ray diffraction and spectroscopy show a crystalline-to-amorphous phase transition. Quantitative modeling of the operando data by Rietveld refinement for X-ray diffraction and multivariate curve resolution (MCR) for X-ray absorption spectroscopy are used in a complementary fashion to track the structural and chemical transitions of both the long-range (crystalline phases) and short-range (including amorphous phases) ordering upon cycling. Scanning X-ray microscopy and full-field nano-tomography visualizes the morphology of electrodes at different electrochemical states with elemental sensitivity to spatially resolve the formation of the Zn- and Mn-containing phases. Overall, this work critically indicates that for Zn/MnO₂ aqueous batteries, the reaction pathways involving Zn-Mn complex formation upon cycling become independent of the polymorphs of the initial electrode and sheds light on the interplay among structural, chemical, and morphological evolution for electrochemically driven phase transitions.