Maiti Sandipan, Pramanik Atin, Mahanty Sourindra
Fuel Cell & Battery Division, Central Glass & Ceramic Research Institute, Council of Scientific and Industrial Research , Kolkata 700032, India.
ACS Appl Mater Interfaces. 2014 Jul 9;6(13):10754-62. doi: 10.1021/am502638d. Epub 2014 Jun 26.
Low electronic conductivity and slow faradic processes limit the performance of MnO2 as an electrochemical pseudocapacitor with respect to cycling and power density. Herein, we report preparation of single-phase α-MnO2, composed of an interconnected nanowire network with "cocoonlike" morphology, and its application as electrode in a symmetric aqueous supercapacitor. Increased "effective" surface area, coexistence of micropores and mesopores, and enhanced electron transport in these nanowire networks result in a specific pseudocapacitance (CS) of 775 F·g(-1) in 3 M KOH, derived from cyclic voltammetry in the potential window of -1 to +1 V at a scan rate of 2 mV·s(-1), the highest reported for two-electrode symmetric configuration. Furthermore, introduction of K4Fe(CN)6 as a redox-active additive to KOH results in ∼7 times increase in energy density at a power density of ∼6000 W·kg(-1). The presence of the Fe(CN)6(4-)/Fe(CN)6(3-) redox couple provides an electron buffer source compensating for the slow faradic reactions. The results demonstrate that this simple approach might be an effective way to enhance the redox kinetics and reversibility of transition metal oxide-based pseudocapacitors.
低电子电导率和缓慢的法拉第过程限制了MnO₂作为电化学赝电容器在循环和功率密度方面的性能。在此,我们报道了由具有“茧状”形态的互连纳米线网络组成的单相α-MnO₂的制备及其作为对称水系超级电容器电极的应用。这些纳米线网络中“有效”表面积的增加、微孔和介孔的共存以及电子传输的增强,在3 M KOH中产生了775 F·g⁻¹的比赝电容(CS),这是通过在-1至+1 V的电位窗口中以2 mV·s⁻¹的扫描速率进行循环伏安法得到的,是两电极对称配置中报道的最高值。此外,将K₄Fe(CN)₆作为氧化还原活性添加剂引入KOH中,在功率密度约为6000 W·kg⁻¹时,能量密度提高了约7倍。Fe(CN)₆⁴⁻/Fe(CN)₆³⁻氧化还原对的存在提供了一个电子缓冲源,以补偿缓慢的法拉第反应。结果表明,这种简单的方法可能是增强基于过渡金属氧化物的赝电容器的氧化还原动力学和可逆性的有效途径。