The CUNY Energy Institute at the City College of New York, Department of Chemical Engineering, Steinman Hall, 140th Street and 160 Convent Avenue, Room 316, New York, New York 10031, USA.
Nat Commun. 2017 Mar 6;8:14424. doi: 10.1038/ncomms14424.
Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g, 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 (BiO)) cathodes intercalated with Cu 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 is shown.
二氧化锰阴极价格低廉，具有 617mAhg 的高理论容量（基于两个电子），这使其成为低成本、高能量密度电池的理想选择。它们与锌等阳极一起用于不可充电电池。目前，在可充电碱性系统中，只有约 10%的理论容量可被利用。使用添加剂来达到全容量的尝试都没有成功。我们报告了一类层状二氧化锰多晶型物（Bi-birnessite）与氧化铋（BiO）混合的 Bi-birnessite 插层阴极，其中嵌入了 Cu，可在超过 6000 次循环中可逆地提供接近全两电子容量。可再充电性的关键在于利用 Cu 的氧化还原电位，在 Bi-birnessite 层状结构的溶解和沉淀过程中可逆地嵌入，从而稳定并增强其电荷转移特性。这个过程有望应用于其他领域，如催化和金属离子嵌入层状结构。我们展示了一个大型棱柱形可充电锌-层状化合物电池，其容量约为 140Whl。
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