Electrochemical voltage spectroscopy for analysis of nickel electrodes

L. Thaller, A. Zimmerman, G. To
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引用次数: 2

Abstract

Electrochemical voltage spectroscopy (EVS) is a technique that directly measures the density of electrochemically active states in an electrode as a function of the applied voltage. In EVS measurements, the voltage of an electrode is scanned at a rate that is slow enough to maintain the electrode close to thermodynamic equilibrium, over a potential range where electroactive species may be oxidized or reduced. The density of reactive sites is obtained from the Coulombs of charge passed through the electrode per voltage increment, which is essentially differential capacitance. For most electrodes, interest is primarily in the Faradaic components of the EVS spectra, which exhibit sharp peaks at the electrochemical redox potentials, although non-Faradaic components (such as double-layer or surface capacitance) can also be measured. For nickel electrodes, EVS provides an extremely useful method for probing the phase composition of the active material based on subtle differences in redox potentials. Alternatively, EVS can detect trace levels of electroactive contaminants in nickel-hydrogen cells or nickel electrodes by scanning the potential over the redox range for the contaminant of interest. We discuss the use of nickel electrode EVS signatures to indicate cobalt additive levels, sinter corrosion, surface changes, double-layer capacitance, electrode swelling, and other factors influencing the performance of the nickel electrode.
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镍电极的电化学电压谱分析
电化学电压谱(EVS)是一种直接测量电极中电化学活性态密度作为施加电压函数的技术。在EVS测量中,以足够慢的速度扫描电极的电压,以保持电极接近热力学平衡,在电活性物质可能被氧化或还原的电位范围内。反应位点的密度由每电压增量通过电极的电荷库仑得到,这本质上是微分电容。对于大多数电极,主要关注EVS光谱的法拉第分量,它在电化学氧化还原电位处表现出尖峰,尽管也可以测量非法拉第分量(如双层或表面电容)。对于镍电极,基于氧化还原电位的细微差异,EVS为探测活性材料的相组成提供了一种非常有用的方法。或者,EVS可以通过扫描氧化还原范围内的电位来检测镍氢电池或镍电极中痕量的电活性污染物。我们讨论了利用镍电极的EVS特征来指示钴添加剂水平、烧结腐蚀、表面变化、双层电容、电极膨胀以及其他影响镍电极性能的因素。
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