The reaction mechanism of α-MnO having 2×2 tunnel structure with zinc ions in a zinc rechargeable battery, employing an aqueous zinc sulfate electrolyte, was investigated by in situ monitoring structural changes and water chemistry alterations during the reaction. Contrary to the conventional belief that zinc ions intercalate into the tunnels of α-MnO , we reveal that they actually precipitate in the form of layered zinc hydroxide sulfate (Zn (OH) (SO )⋅5 H O) on the α-MnO surface. This precipitation occurs because unstable trivalent manganese disproportionates and is dissolved in the electrolyte during the discharge process, resulting in a gradual increase in the pH value of the electrolyte. This causes zinc hydroxide sulfate to crystallize from the electrolyte on the electrode surface. During the charge process, the pH value of the electrolyte decreases due to recombination of manganese on the cathode, leading to dissolution of zinc hydroxide sulfate back into the electrolyte. An analogous phenomenon is also observed in todorokite, a manganese dioxide polymorph with 3×3 tunnel structure that is an indication for the critical role of pH changes of the electrolyte in the reaction mechanism of this battery system.

The intercalation mechanism of zinc ions into 2 × 2 tunnels of an α-MnO2 cathode for rechargeable zinc batteries was revealed. It involves a series of single and two-phase reaction steps and produces buserite, a layered compound with an interlayer spacing of 11 Å as a discharge product.

Zn-ion batteries are emerging energy storage systems eligible for large-scale applications, such as electric vehicles. These batteries consist of totally environmentally-benign electrode materials and potentially manufactured very economically. Although Zn/α-MnO2 systems produce high energy densities of 225 Wh kg−1, larger than those of conventional Mg-ion batteries, they show significant capacity fading during long-term cycling and suffer from poor performance at high current rates. To solve these problems, the concrete reaction mechanism between α-MnO2 and zinc ions that occur on the cathode must be elucidated. Here, we report the intercalation mechanism of zinc ions into α-MnO2 during discharge, which involves a reversible phase transition of MnO2 from tunneled to layered polymorphs by electrochemical reactions. This transition is initiated by the dissolution of manganese from α-MnO2 during discharge process to form layered Zn-birnessite. The original tunneled structure is recovered by the incorporation of manganese ions back into the layers of Zn-birnessite during charge process.

Herein, we evaluate the detailed insertion mechanism of aluminum ions into the Mo6S8 Chevrel phase in the 1-ethyl-3-methylimidazolium tetrachloroaluminate ionic liquid through combined structural and electrochemical characterization. This involves two-step two-phase insertion reactions, where the first and the second step account for 3/4 and 1/4 of the total reversible capacity, respectively. During the first step, aluminum ions occupy the inner ring sites in the Chevrel phase, forming AlMo6S8 with a higher activation energy for cation diffusion. Subsequently, Al4/3Mo6S8 emerges as a discharge product during the second step, where one aluminum ion fills one outer ring site in every three AlMo6S8 units. The diffusion coefficient for aluminum ions through the Chevrel phase was found much lower than that of lithium or magnesium ions, reflecting the difficulties in redistributing trivalent charge carried by each aluminum ion.