(232ab) On the Electrical Double Layers of Multi-Component Electrolytes
AIChE Annual Meeting
2016 AIChE Annual Meeting
Engineering Sciences and Fundamentals
Poster Session: Interfacial Phenomena (Area 1C)
Monday, November 14, 2016 - 3:15pm to 5:45pm
Recently, Yamagata et al. have reported in their electrochemical measurement using carbon materials as the electrode and ionic liquids as the electrolyte that the capacitance dramatically increases in the negative potential range when a lithium salt is added to the electrolyte as the second component . They have also shown that, with the addition of a lithium salt, the potential window is enhanced. This example shows that the electrochemical behaviors of two-component electrolytes can be fundamentally different from those of one-component electrolytes. Since the increase of capacitance is observed within the potential window, such behaviors are speculated to be caused by the change in the molecular structure in the electrical double layer. In order to clarify the relation between the electrochemical behavior and the molecular structure in the electrical double layer, we performed Monte Carlo simulation using simple models. The two components of ions were discriminated by the size of the cations.
The analysis of the ionic structure showed that the electrical double layer on the cathode is dominantly formed by the larger cations under small negative potentials, while they are replaced by the smaller cations under large negative potentials . This transition of the ionic structure with electrode potential is also consistent with the enhancement of the potential window that was found in the experimental work, which suggests that the organic cations are expelled from the electrical double layer under large negative potentials and the chance of decomposition is reduced. The results of the Monte Carlo simulation qualitatively reproduced the experimentally observed electrochemical behaviors of the two-component electrolytes. The mechanism of the observed structural transition with potential can be explained in terms of the competition between the electrostatic interaction of ions with the electrode and that among the ions alone [2,3]. The results are also consistent with the previous simulation results of two-component electrolytes near the electrode .  M. Yamagata, N. Nishigaki, S. Nishishita, Y. Matsui, T. Sugimoto, M. Kikuta, T. Higashizaki, M. Kono, and M. Ishikawa, Electrochim. Acta, 110, 181 (2013).  K. Kiyohara, M. Yamagata, M. Ishikawa, J. Chem. Phys., 144, 134701 (2016).
 K. Kiyohara, H. Shioyama, T. Sugino, K. Asaka, Y. Soneda, K. Imoto, and M. Kodama, J. Chem. Phys., 138, 234704 (2013)
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