Asymmetric Rectified Electric Fields for Symmetric Electrolytes

• Published in: Langmuir Vol. 40; no. 27; pp. 14066 - 14075
• Main Authors: Barnaveli, A., van Roij, R.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09-07-2024
• ISSN: 0743-7463; 1520-5827; 1520-5827
• DOI: 10.1021/acs.langmuir.4c01516

In this paper, building upon the numerical discovery of asymmetric rectified electric fields (AREFs), we explore the generation of AREF by applying a sawtooth-like voltage to 1:1 electrolytes with equal diffusion coefficients confined between two planar blocking electrodes. This differs from an earlier approach based on a sinusoidal AC voltage applied to 1:1 electrolytes with unequal diffusion coefficients. By numerically solving the full Poisson–Nernst–Planck equations, we demonstrate that AREF can be generated by a slow rise and a fast drop of the potential (or vice versa), even for electrolytes with equal diffusion coefficients of the cations and anions. We employ an analytically constructed equivalent electric circuit to explain the underlying physical mechanism. Importantly, we find that the strength of AREF can be effectively tuned from zero to its maximal value by only manipulating the time dependence of the driving voltage, eliminating the necessity to modify the electrolyte composition between experiments. This provides valuable insights to control the manipulation of AREF, which facilitates enhanced applications in diverse electrochemical systems.