Rechargeable batteries based on MnO2 cathodes, able to operate in mild aqueous electrolytes, have attracted attention due to their appealing features for the design of low‐cost stationary energy storage devices. However, the charge/discharge mechanism of MnO2 in such media is still a matter of debate. Here, an in‐depth quantitative spectroelectrochemical analysis of MnO2 thin‐films provides a set of unrivaled mechanistic insights. A major finding is that charge storage occurs through the reversible two‐electron faradaic conversion of MnO2 into Mn2+ in the presence of a wide range of weak Brønsted acids, including the [Zn(H2O)6]2+ or [Mn(H2O)6]2+ complexes present in aqueous Zn/MnO2 batteries. Furthermore, it is shown that buffered electrolytes loaded with Mn2+ are ideal to achieve highly reversible conversion of MnO2 with both high gravimetric capacity and remarkably stable charging/discharging potentials. In the most favorable case, a record gravimetric capacity of 450 mA·h·g−1 is obtained at a high rate of 1.6 A·g−1, with a Coulombic efficiency close to 100% and a MnO2 utilization of 84%. Overall, the present results challenge the common view on MnO2 the charge storage mechanism in mild aqueous electrolytes and underline the benefit of buffered electrolytes for high‐performance rechargeable aqueous batteries.
Crystalline structures and lattice water molecules are believed to strongly influence the ability of metal oxides to reversibly and rapidly insert protons in aqueous batteries. In the present work, we performed a systematic analysis of the electrochemical charge storage properties of nanostructured TiO 2 electrodes composed of either anatase or amorphous TiO 2 in a mild buffered aqueous electrolyte. We demonstrate that both materials allow reversible bulk proton insertion up to a maximal reversible gravimetric capacity of 150 mA•h•g -1 . We also show that the TiO 2 crystallinity governs the energetics of the charge storage process, with a phase transition for anatase, while having little effect on either the interfacial charge-transfer kinetics or the apparent rate of proton diffusivity within the metal oxide. Finally, with both TiO 2 electrodes, reversible proton insertion leads to gravimetric capacities as high as 95 mA•h•g -1 at 75 C. We also reveal two competitive reactions decreasing the Coulombic efficiency at low rates, i.e. hydrogen evolution and a nonfaradaic self-discharge reaction. Overall, this work provides a comprehensive overview of the proton-coupled electrochemical reactivity of TiO 2 and highlights the key issues to be solved in order to truly benefit from the unique properties of protons as fast charge carriers in metal oxides.
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