Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 122, Issue 21, Pages 11177-11185Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.7b11685
Keywords
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Funding
- Advanced Research Projects Agency-Energy (ARPA-E), U.S. Department of Energy [DE-AR0000535]
- National Science Foundation [ACI-1053575, ECCS-1542148]
- National Science Foundation Major Research Instrumentation Program [CHE-1338173]
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This work reports rechargeable Zn/beta-MnO2 alkaline batteries as promising stationary energy storage. Unlike commercial alkaline batteries with poor cyclic performance, the nanosized beta-MnO2 cathode in the mixture of LiOH and KOH electrolyte enables rechargeable reactions with high capacity. To unveil the underlying reaction mechanisms of nanosized beta-MnO2, we combine thermodynamic frameworks with experimental characterization, including electrochemistry, X-ray diffraction, and X-ray photoelectron spectroscopy. The results demonstrate a series of proton intercalation reaction (beta-MnO2 -> gamma-MnOOH) and two-phase conversion reactions (gamma-MnOOH -> Mn-(OH)(2) -> lambda-MnO2) during the first cycle and Li and H cointercalation in the host structure of lambda-MnO2 spinel during the 100th cycle. It is remarkable that the addition of Bi2O3 in the nanosized beta-MnO2 cathode exhibits outstanding capacity. After 100 dischargings, the battery demonstrates a capacity of 316 mA h g(-1). Our findings can serve in the tailored cathode design in high capacity and rechargeable Zn/beta-MnO2 alkaline batteries.
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