Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes

ACS Appl Mater Interfaces. 2023 Aug 23;15(33):39905-39914. doi: 10.1021/acsami.3c08543. Epub 2023 Aug 11.

Abstract

Ionic diode based devices or circuits can be applied, for example, in electroosmotic pumps or in desalination processes. Aquivion ionomer coated asymmetrically over a Teflon film (5 μm thickness) with a laser-drilled microhole (approximately 10 μm diameter) gives a cationic diode with a rectification ratio of typically 10-20 (measured in 0.01 M NaCl with ±0.3 V applied bias). Steady state voltammetry, chronoamperometry, and electrochemical impedance spectroscopy data are employed to characterize the ionic diode performance parameters. Next, a COMSOL 6.0 finite element model is employed to quantitatively assess/compare transient phenomena and to extract mechanistic information by comparison with experimental data. The experimental diode time constant and diode switching process associated with a distorted semicircle (with a typical diode switching frequency of 10 Hz) in the Nyquist plot are reproduced by computer simulation and rationalized in terms of microhole diffusion-migration times. Fundamental understanding and modeling of the ionic diode switching process can be exploited in the rational/optimized design of new improved devices.

Keywords: accumulation−depletion; desalination; diffusion−migration; electrochemical impedance spectroscopy; ionic diode.