Institute of Physics, Technical University of Lodz, ul. Wolczanska 219, 90-924 Lodz, Poland.
J Chem Phys. 2010 Jun 14;132(22):224901. doi: 10.1063/1.3447893.
The electrical impedance of an insulating solid containing ions is evaluated in the presence of the generation and recombination of ions. The case of perfectly blocking electrodes is considered. It is shown that in the case where the diffusion coefficients of the positive and negative ions are equal, the expression for the electrical impedance coincides with the one valid in the absence of the generation and recombination of ions, with the bulk density of ions fixed by the chemical reaction describing the generation and recombination of ions. In particular, in the low frequency region, the resistance tends to the value corresponding to the plateau, and the reactance diverges as the inverse of the frequency. The case where the neutral particles, that by decomposition generate the ions, and the positive ions have a vanishing small diffusion coefficient with respect to that of the negative ions is also considered. In this situation, in the series representation, the resistance of the cell presents two plateaus. One in the low frequency region is related to the generation-recombination phenomenon. The other, with a resistance smaller than the previous one, ends at the frequency of Debye. This result is of some importance because it could be the mechanism able to explain the experimental data obtained with hydrogels doped with KCl.
在存在离子产生和复合的情况下,评估了含有离子的绝缘固体的电导率。考虑了完全阻挡电极的情况。结果表明,在正、负离子扩散系数相等的情况下,电导率的表达式与不存在离子产生和复合的情况下的表达式相同,此时离子的体密度由描述离子产生和复合的化学反应固定。特别是在低频区域,电阻趋于与平台对应的数值,电抗随频率的倒数发散。还考虑了中性粒子(通过分解产生离子)和正离子相对于负离子的扩散系数可以忽略不计的情况。在这种情况下,在串联表示中,电池的电阻呈现出两个平台。一个在低频区域与产生-复合现象有关。另一个,电阻小于前一个,在德拜频率处结束。这个结果很重要,因为它可能是能够解释用 KCl 掺杂水凝胶获得的实验数据的机制。