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Sci Rep. 2014 Aug 14;4:6066. doi: 10.1038/srep06066.

Electrochemically-induced reversible transition from the tunneled to layered polymorphs of manganese dioxide.

Author information

1
Center for Energy Convergence Research, Korea Institute of Science and Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul, 136-791, Korea.
2
Department of Materials Science and Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul, 133-791, Korea.

Abstract

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.

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