Reducing Manganese Dissolution in Electrolytic Manganese Dioxide Electrodes in NaOH Electrolyte

Xinsheng Wu, Jay Whitacre
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Abstract

Previous attempts to enhance the stability and performance of MnO2-based cathodes for use in aqueous alkaline electrolytes, primarily KOH-based, have relied on a range of additives. This work demonstrates that the fast capacity decay of the MnO2-based cathode materials in alkaline electrolytes is mainly due to spontaneous manganese dissolution when cycling through the second-electron reaction voltage range. Reducing relative electrolyte content and using carbon materials that have a high specific surface area suppresses manganese dissolution and thus extends the cycle life of the electrode material while reducing overall battery costs. Moreover, reducing the size of the MnO2 particles and decreasing the cycling rate are found to increase manganese dissolution and negatively impact the performance of the electrode material, indicating a sensitivity to material surface area. Lastly, Fe-MnO2-based low-cost battery chemistry was also demonstrated based on the second electron reaction of the MnO2 in an electrolyte lean environment, which could be promising for grid-level energy storage.
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降低电解二氧化锰电极在 NaOH 电解液中的锰溶解度
以往在水基碱性电解质(主要是以 KOH 为基质的电解质)中使用二氧化锰基阴极材料时,为了提高其稳定性和性能,曾尝试使用一系列添加剂。这项研究表明,MnO2 基阴极材料在碱性电解质中的容量快速衰减主要是由于在二次电子反应电压范围内循环时锰自发溶解造成的。降低相对电解质含量和使用具有高比表面积的碳材料可以抑制锰溶解,从而延长电极材料的循环寿命,同时降低电池的总体成本。此外,研究还发现,减小 MnO2 颗粒的尺寸和降低循环速率会增加锰的溶解,并对电极材料的性能产生负面影响,这表明了对材料表面积的敏感性。最后,基于二氧化锰在电解质贫化环境中的二次电子反应,还展示了基于铁-二氧化锰的低成本电池化学,这对电网级能源存储大有可为。
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