Influence of experimental conditions on the electrochemical window. Case study on bis(trifluoromethylsulfonyl)imide-based ionic liquids

Gancarz, Paweł; Zorębski, Edward; Dzida, Marzena

doi:10.1016/j.elecom.2021.107107

Cited by 19 publications

(18 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…aDynamic viscosity η ; density ρ ; concentration c ; diffusion coefficients of cations ( D + ) and anions ( D − ); specific conductivity σ measured via impedance spectroscopy; molar conductivities calculated by Λ NMR = ( D + + D − )· N A · e 2 · k −1 · T −1 and Λ imp = σ · M · ρ −1 ; ionicity I = Λ imp · Λ NMR −1 ; cathodic and anodic limits E c and E a ; electrochemical window Δ E = E a − E c .b E c and E a are calibrated against Fc/Fc + ; details on the measurements and the assessment of the electrochemical limits 97,98 are summarized in the ESI.cLiterature values. 34 dLiterature value at 15 °C: 10.76 mS cm −1 and at 25 °C: 15.46 mS cm −1 .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Cyano(fluoro)borate and cyano(hydrido)borate ionic liquids: low-viscosity ionic media for electrochemical applications

Riefer

Zapf

Sprenger

et al. 2023

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

“…b E c and E a are calibrated against Fc/Fc + ; details on the measurements and the assessment of the electrochemical limits 97,98 are summarized in the ESI.…”

Section: Resultsmentioning

confidence: 99%

Cyano(fluoro)borate and cyano(hydrido)borate ionic liquids: low-viscosity ionic media for electrochemical applications

Riefer

Zapf

Sprenger

et al. 2023

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…CV was performed on both platinum and gold TFEs to examine the behavior of the oxygen/superoxide (O 2 /O 2 •– ) redox couple on different electrode surfaces. It is already well-known that the electrode material can influence the electrochemical windows − and electrochemical properties of dissolved analytes, and oxygen reduction has been widely characterized on different electrodes in various pure ILs. ,,,, …”

Section: Resultsmentioning

confidence: 99%

Mixing Ionic Liquids Affects the Kinetics and Thermodynamics of the Oxygen/Superoxide Redox Couple in the Context of Oxygen Sensing

Mullen

Silvester

2022

ACS Phys. Chem Au

View full text Add to dashboard Cite

The electrochemical oxygen reduction reaction is vital for applications such as fuel cells, metal air batteries and for oxygen gas sensing. Oxygen undergoes a 1-electron reduction process in dry ionic liquids (ILs) to form the electrogenerated superoxide ion that is solvated and stabilized by IL cations. In this work, the oxygen/superoxide (O 2 /O 2•− ) redox couple has been used to understand the effect of mixing ILs with different cations in the context of developing designer electrolytes for oxygen sensing, by employing cyclic voltammetry at both gold and platinum electrodes. Different cations with a range of sizes, geometries and aromatic/aliphatic character were studied with a common bis(trifluoromethylsulfonyl)imide ([NTf 2 ] − ) anion. Diethylmethylsulfonium ([S 2,2,1 ] + ), N-butyl-N-methylpyrrolidinum ([C 4 mpyrr] + ) and tetradecyltrihexylphosphonium ([P 14,6,6,6 ] + ) cations were mixed with a common 1-butyl-3-methylimidazolium ([C 4 mim] + ) cation at mole fractions (x) of [C 4 mim] + of 0, 0.2, 0.4, 0.6, 0.8, and 1. Both the redox kinetics and thermodynamics were found to be highly dependent on the cation structure and the electrode material used. Large deviations from "ideal" mixtures were observed for mixtures of [C 4 mim][NTf 2 ] with [C 4 mpyrr][NTf 2 ] on gold electrodes, suggesting a much higher amount of [C 4 mim] + ions near the electrode surface despite the large excess of [C 4 mpyrr] + in the bulk. The electrical double layer structure was probed for a mixture of [C 4 mim] 0.2 [C 4 mpyrr] 0.8 [NTf 2 ] using atomic force microscopy measurements on Au, revealing that the first layer was more like [C 4 mim][NTf 2 ] than [C 4 mpyrr][NTf 2 ]. Unusually fast kinetics for O 2 /O 2 •− in mixtures of [C 4 mim] + with [ P 14,6,6,6 ] + were also observed in the electrochemistry results, which warrants further follow-up studies to elucidate this promising behavior. Overall, it is important to understand the effect on the kinetic and thermodynamic properties of electrochemical reactions when mixing solvents, to aid in the creation of designer electrolytes with favorable properties for their intended application.

show abstract

“…From the literature, we selected synthetically accessible cations and anions used in the study of ILs, − ,, respectively, 138 and 40 ions. The chosen cations are composed by the following chemical species: N, Cl, F, Si, C, S, Br, P, O, I, and H atoms, while the anions are composed by O, I, As, N, H, C, Sb, Cl, S, F, Ga, In, B, Br, Nb, Al, P, Ta, and Si atoms.…”

Section: Theoretical Approach and Computational Detailsmentioning

confidence: 99%

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

Moraes¹,

Pinheiro

Lourenço

et al. 2022

J. Chem. Inf. Model.

View full text Add to dashboard Cite

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.

show abstract

Influence of experimental conditions on the electrochemical window. Case study on bis(trifluoromethylsulfonyl)imide-based ionic liquids

Cited by 19 publications

References 41 publications

Cyano(fluoro)borate and cyano(hydrido)borate ionic liquids: low-viscosity ionic media for electrochemical applications

Cyano(fluoro)borate and cyano(hydrido)borate ionic liquids: low-viscosity ionic media for electrochemical applications

Mixing Ionic Liquids Affects the Kinetics and Thermodynamics of the Oxygen/Superoxide Redox Couple in the Context of Oxygen Sensing

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

Contact Info

Product

Resources

About