Electrical Double Layer at Various Electrode Potentials: A Modification by Vibration

Electrical Double Layer at Various Electrode Potentials: A Modification by Vibration
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DOI:
10.1021/acs.jpcc.7b00961
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发表时间:
2017-02
影响因子:
3.7
通讯作者:
H. Zhan;J. Červenka;S. Prawer;D. J. Garrett
H. Zhan;J. Červenka;S. Prawer;D. J. Garrett
中科院分区:
化学3区
文献类型:
--
作者:
H. Zhan;J. Červenka;S. Prawer;D. J. Garrett

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This paper proposes a vibration model of ions as an improvement over the conventional Gouy–Chapman–Stern theory, which is used to model the electrical double layer capacitance and to study the ionic dynamics at electrode/electrolyte interfaces. Although the Gouy–Chapman–Stern model is successful for small applied potentials, it fails to explain the observed behavior at larger potentials, which are becoming increasingly important as materials with high charge injection capacities are developed. A time-dependent study on ionic transport indicates that ions vibrate near the electrode surface in response to the applied electric field. This vibration allows us to correctly predict the experimentally observed decreasing differential capacitance at high electrode potential. This new model elucidates the mechanism behind the ionic dynamics at solid–electrolyte interfaces, providing useful insight that may be applied to many electrochemical systems in energy storage, photoelectrochemical cells, and biosensing.