Rechargeable magnesium batteries (RMBs), with Cu as positive electrode current collector (CC), typically display a gradual capacity increase with cycling. Whereas the origin of this was suggested in gradual active material electro‐activation, the fact that this is prevalent in many positive electrode material systems remains unexplained. Herein, we elucidate the underlying mechanism through a series of multiscale joint operando X‐ray characterizations, including operando synchrotron X‐ray diffraction and imaging technology. We select a series of manganese oxides as benchmark positive electrodes and find that no magnesium ions are stored within the lattices of these materials, despite an apparent cell capacity increase with cycling. The origin of capacity increase is rooted in the gradual electrochemical corrosion of metallic Cu, release of Cu(I, II) species in electrolyte, and their subsequent redox activity, resulting in apparent electrode capacity gains. Furthermore, the shuttle and redox speciation of Cu ions trigger the irreversible depletion of both the Cu CC (or any other source) and the magnesium metal, ultimately leading to cell failure. Our work suggests the need to reconsider the appropriateness of using Cu as a positive electrode CC for RMBs.
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