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首页> 外文期刊>Electrochimica Acta >A new experimental approach to the time-constants of electrochemical impedance: frequency response of the double layer capacitance
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A new experimental approach to the time-constants of electrochemical impedance: frequency response of the double layer capacitance

机译：电化学阻抗时间常数的新实验方法：双层电容的频率响应

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摘要

Modeling of electrochemical impedance is, generally, realized by calculating the faradaic impedance on the basis of the reaction mechanism involving adsorbed reaction intermediates, then connecting it in parallel to a constant interfacial capacitance. If this procedure is largely used, one may consider it arbitrary, and it is essential to verify whether the double layer capacitance is actually independent or not of dc and ac currents. In order to measure this coupling, an original experimental setup was devised that allowed measurement of the variation of double layer capacitance induced by a low frequency ac perturbing signal used for the electrode impedance measurements Z(ω). The latter was measured between 100 Hz and 100μHz as a classical way. The modulation of the double layer capacitance ΔC(ω)/ΔE at 1 kHz was measured simultaneously by coupling a lock-in amplifier to a classical experimental setup. The electrochemical interface examined was a rotating disk of iron in 1 M Na{sub}2SO{sub}4 acidified at pH 4. A close correlation between Z(ω) and ΔC(ω)/ΔE was found. This is, in our knowledge the first investigation of the modulation of the double layer capacitance together with the impedance measurements. As for the very origin of the relaxation time constant of the double layer capacitance, more detailed experiments are necessary.
机译：通常，通过基于涉及吸附的反应中间体的反应机理计算法拉第阻抗，然后将其并联连接至恒定的界面电容，来实现电化学阻抗的建模。如果大量使用此程序，则可以认为它是任意的，并且必须验证双层电容实际上是否独立于直流电流和交流电流。为了测量这种耦合，设计了一种原始的实验装置，该装置允许测量由用于电极阻抗测量Z（ω）的低频交流扰动信号引起的双层电容的变化。后者以经典方式在100 Hz和100μHz之间测量。通过将锁定放大器耦合到经典实验装置，同时测量了1 kHz时双层电容ΔC（ω）/ΔE的调制。检验的电化学界面是铁的旋转盘，在1 M Na {sub} 2SO {sub} 4中在pH 4下酸化。发现Z（ω）与ΔC（ω）/ΔE之间具有密切的相关性。据我们所知，这是对双层电容调制以及阻抗测量的首次研究。至于双层电容的弛豫时间常数的起源，有必要进行更详细的实验。

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