Screening of the Role of the Chemical Structure in the Electrochemical Stability Window of Ionic Liquids: DFT Calculations Combined with Data Mining.

Ionic liquids have attracted the attention of researchers as possible electrolytes for electrochemical energy storage devices. However, their properties, such as the electrochemical stability window (ESW), ionic conductivity, and diffusivity, are influenced both by the chemical structures of cations and anions and by their combinations. Most studies in the literature focus on the understanding of common ionic liquids, and little effort has been made to find ways to improve our atomistic understanding of those systems. The goal of this paper is to explore the structural characteristics of cations and anions that form ionic liquids that can expand the HOMO/LUMO gap, a property directly linked to the ESW of the electrolyte. For that, we design a framework for randomly generating new ions by combining their fragments. Within this framework, we generate about 104 cations and 104 anions and fully optimize their structures using density functional theory. Our calculations show that aromatic cations are less stable ionic liquids than aliphatic ones, an expected result if chemical rationale is used. More importantly, we can improve the gap by adding electron-donating and electron-withdrawing functional groups to the cations and anions, respectively. The increase can be about 2 V, depending on the case. This improvement is reflected in a wider ESW.

Numerical Resolving of Net Faradaic Current in Fast-Scan Cyclic Voltammetry Considering Induced Charging Currents.

In this paper, we study theoretically and experimentally the effect of induced charging currents on the fast-scan cyclic voltammetry. As explained in this paper, the phenomenon originates from the coupling between faradaic and capacitive currents in the presence of uncompensated resistance. Due to the existence of induced charging currents, the capacitive contribution to the total current is different from the capacitive current measured in the absence of electroactive species. In this paper, we show that this effect is particularly important when the ratio of the capacitive current and the total current is close to unity, even for a relatively low cell time constant. Consequently, the conventional background subtraction method may be inaccurate in these situations. In this work, we develop a method that separates the faradaic and capacitive currents, combining simulation and experimental data. The method is applicable even in the presence of potential-dependent capacitance. The theoretical results are compared with some previously reported results and with experiments carried out on the potassium ferrocyanide/ferricyanide redox couple. Platinum disk electrodes of different diameters and NaClO4 support electrolyte of different concentrations were used to obtain different cell time constants. The proposed method allowed us to separate the real capacitive current even in the situations where the conventional background subtraction used in many published papers is clearly inappropriate.