Jinchao Huang

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries.

Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g−1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ∼10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cu to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ∼140 Wh l−1 is shown.

A conversion-based highly energy dense Cu2+ intercalated Bi-birnessite/Zn alkaline battery

Manganese dioxide (MnO2)–zinc (Zn) batteries are cheap and environmentally benign and have sufficient theoretical energy density to be used as an energy storage device for the grid; however, they have been relegated to primary systems, where the complete energy is delivered in a single discharge, due to the irreversibility of their active materials. Until recently, rechargeable MnO2–Zn batteries have only been able to cycle ∼10% of MnO2s theoretical 2-electron capacity (617 mA h g−1), thus delivering significantly reduced energy density. In a recent paper from our group, we reversibly accessed the full theoretical 2-electron capacity of MnO2 for >6000 cycles by using a layered polymorph of MnO2 mixed with bismuth oxide (Bi2O3) called Bi-birnessite (Bi–δ-MnO2) intercalated with Cu2+ ions. This discovery highlighted the possibility of achieving very high energy densities from inexpensive aqueous batteries; however, a full-cell demonstration with Zn as the anode was not studied. Here we report for the first time the effect of Zn anodes on the cycle life and energy density of a full cell, where we observe that 15% depth-of-discharge (DOD) of the Zns theoretical capacity (820 mA h g−1) creates a cell energy density of ∼160 W h L−1; however, this causes a drastic shape change and formation of irreversible zinc oxide (ZnO) at the anode, which ultimately causes cell failure after ∼100 cycles. A drop in energy density is also observed as a result of the interaction of dissolved Zn ions with the cathode, which forms a resistive Zn-birnessite compound in the early cycles, and then forms a highly resistive haeterolite (ZnMn2O4) in the later cycles, and ultimately causes cathode failure. A possible solution using a calcium hydroxide layer as a separator is presented, where the layer blocks the interaction of zinc ions through a complexing mechanism to obtain >900 cycles with >80% retention of MnO2 DOD.