Effect of dissolved LiCl on the ionic liquid–Au(111) electrical double layer structure

Hayes, Robert A.; Borisenko, Natalia; Corr, Brendan; Webber, Grant B.; Endres, Frank; Atkin, Rob

doi:10.1039/c2cc35737b

Cited by 78 publications

(99 citation statements)

References 33 publications

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“…The rather low rate of electrodeposition using the TFSI precursor and the large overpotentials required might be related to the interfacial structure in this ionic liquid. It has been shown recently that in ionic liquids very strong interfacial layers can form that hinder electroactive ions to approach the electrode closely enough for rapid reduction (22,23). Additives might disturb the interfacial structure and enable the reaction (22).…”

Section: Discussionmentioning

confidence: 99%

“…It has been shown recently that in ionic liquids very strong interfacial layers can form that hinder electroactive ions to approach the electrode closely enough for rapid reduction (22,23). Additives might disturb the interfacial structure and enable the reaction (22). Therefore further experiments on La deposition using different additive ions shall be carried out in order to accelerate the deposition.…”

Section: Discussionmentioning

confidence: 99%

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Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

Asen

Mostafa

et al. 2016

ECS Trans.

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Electrochemical deposition was studied as a potentially scalable method for the preparation of Pt-rare earth alloys for application as cathode catalyst in proton exchange membrane fuel cells. For this purpose, experiments both on electrodeposition of platinum and of the rare earth elements yttrium and lanthanum were carried out in two different types of ionic liquid. While the electrodeposition of platinum was successful in both liquids, the deposition of the rare earth metals was more challenging. The deposition of Y in a TFSI based liquid was prevented by electrode passivation, while in a BF4 -liquid no passivation was seen, but also no clear indication of a deposition process was seen. For La, there was deposition using different precursors, but only at very low deposition rates. The nature of the deposit could not yet be unequivocally determined. Initial attempts in alloy deposition were not successful.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

Asen

Mostafa

et al. 2016

ECS Trans.

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“…Recently, the solid-liquid interface has been explored in the presence of lithium salts. [20][21][22][23][24][25] In situ STM revealed that an underpotential deposition (UPD) of Li …”

Section: Introductionmentioning

confidence: 99%

“…In situ AFM showed that the addition of 0.05 wt% LiCl in 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIm]FAP) influences significantly the interfacial structure: an attractive force is obtained in the presence of LiCl, while a repulsive force is measured for the pure ionic liquid 21. Furthermore, in situ STM revealed that by reducing the V vs. Pt quasi ref.…”

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confidence: 98%

[Py_1,4]FSI-NaFSI-Based Ionic Liquid Electrolyte for Sodium Batteries: Na⁺ Solvation and Interfacial Nanostructure on Au(111)

et al. 2016

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In this paper, the NaFSI-[Py 1,4 ]FSI/Au(111) interface was investigated using cyclic voltammetry (CV) and in situ atomic force microscopy (AFM). Raman spectroscopy was used to evaluate the Na + solvation in [Py 1,4 ]FSI. It was found that Na coordinates with three FSIforming [Na(FSI) 3 ] 2-. In situ AFM revealed that the interaction of [Py 1,4 ]FSI with Au (111) is much stronger compared to other ionic liquids measured using the same technique. On applying a potential, a force of about 50 nN is required to penetrate through the innermost layer. On addition of low concentration of NaFSI (0.05 M), an insignificant change in the innermost solvation layer was observed, whereas on addition of 0.25 M and 0.5 M NaFSI, a significant change in the interfacial structure was noted. The present study clearly shows that Na + ions vary the ionic liquid/Au(111) interface and could provide insight into the interfacial processes in ionic liquid based sodium batteries.

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“…52 These experiments reveal the arrangement of IL cations and anions on the surface for potentials between ± 0.3 V, as well as how added Li + or Cl -affects the Stern layer structure.…”

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confidence: 98%

Nanostructure of the Ionic Liquid–Graphite Stern Layer

et al. 2015

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Ionic liquids (ILs) are attractive solvents for devices such as lithium ion batteries and capacitors, but their uptake is limited, partially because their Stern layer nanostructure is poorly understood compared to molecular solvents. Here, in situ amplitude-modulated atomic force microscopy has been used to reveal the Stern layer nanostructure of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm TFSI)-HOPG (highly ordered pyrolytic graphite) interface with molecular resolution. The effect of applied surface potential and added 0.1 wt/wt % Li TFSI or EMIm Cl on ion arrangements is probed between ±1 V. For pure EMIm TFSI at open-circuit potential, well-defined rows are present on the surface formed by an anion-cation-cation-anion (A-C-C-A) unit cell adsorbed with like ions adjacent. As the surface potential is changed, the relative concentrations of cations and anions in the Stern layer respond, and markedly different lateral ion arrangements ensue. The changes in Stern layer structure at positive and negative potentials are not symmetrical due to the different surface affinities and packing constraints of cations and anions. For potentials outside ±0.4 V, images are featureless because the compositional variation within the layer is too small for the AFM tip to detect. This suggests that the Stern layer is highly enriched in either cations or anions (depending on the potential) oriented upright to the surface plane. When Li(+) or Cl(-) is present, some Stern layer ionic liquid cations or anions (respectively) are displaced, producing starkly different structures. The Stern layer structures elucidated here significantly enhance our understanding of the ionic liquid electrical double layer.

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Effect of dissolved LiCl on the ionic liquid–Au(111) electrical double layer structure

Cited by 78 publications

References 33 publications

Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

[Py_1,4]FSI-NaFSI-Based Ionic Liquid Electrolyte for Sodium Batteries: Na⁺ Solvation and Interfacial Nanostructure on Au(111)

Nanostructure of the Ionic Liquid–Graphite Stern Layer

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Effect of dissolved LiCl on the ionic liquid–Au(111) electrical double layer structure

Cited by 78 publications

References 33 publications

Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

Electrodeposition of Pt - Rare Earth Alloys as ORR Catalysts for Fuel Cells

[Py1,4]FSI-NaFSI-Based Ionic Liquid Electrolyte for Sodium Batteries: Na+ Solvation and Interfacial Nanostructure on Au(111)

Nanostructure of the Ionic Liquid–Graphite Stern Layer

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[Py_1,4]FSI-NaFSI-Based Ionic Liquid Electrolyte for Sodium Batteries: Na⁺ Solvation and Interfacial Nanostructure on Au(111)