Evaluation of static differential capacitance at the [C4mim+][TFSA−]/electrode interface using molecular dynamics simulation combined with electrochemical surface plasmon resonance measurements

Zhang, Shiwei; Nishi, Naoya; Katakura, Seiji; Sakka, Tetsuo

doi:10.1039/d1cp01435h

Cited by 14 publications

(19 citation statements)

References 88 publications

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“…S2a) [33]. The negative Δθ shift reflects a lower local refractive index for the cation rich ionic layer in the EDL than for the anion rich counterpart, which was revealed by our recent study combining ESPR and molecular dynamics simulation [42]. After the negative shift, Δθ switched to a positive shift at potentials where the cathodic deposition occurs (<−0.7 V).…”

Section: -4 Simulation Of Resonance Angle Shiftmentioning

confidence: 78%

In Situ Surface Roughness Analysis of Electrodeposited Co Films in an Ionic Liquid Using Electrochemical Surface Plasmon Resonance: Effect of Leveling Additives

Nishi

Ezawa

Sakka

2021

J. Electrochem. Soc.

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The effect of two leveling additives, thiourea (TU) and coumarin (CM), on cobalt electrodeposition process in an ionic liquid (IL), 1-butyl-3methylimidazolium bis(trifluoromethanesulfonyl)amide (C4mimTFSA), at the gold surface has been analyzed in-situ using electrochemical surface plasmon resonance (ESPR), in which the SPR resonance angle (Δθ) has been recorded simultaneously with cyclic voltammograms. The two additives show Δθ behaviors different from the additive-free case and from each other. In the case of TU, the positive Δθ shift due to Co cathodic deposition is larger than the additive-free case. Even after the subsequent negative Δθ shift due to Co anodic dissolution, Δθ remains positive not returning to the original value. This indicates that the dissolution of gold facilitated by TU roughens the surface of the gold electrode. In contrast, in the case of CM, the positive Δθ shift due to -2 -Co cathodic deposition is smaller than the additive-free case. A model analysis using Fresnel reflectivity has revealed that CM actually smooths the surface of the Co film even in the initial process of the electrodeposition. These findings illustrate that ESPR can sense in-situ the surface roughness change during electrodeposition on the order of Å.

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Section: -4 Simulation Of Resonance Angle Shiftmentioning

confidence: 78%

In Situ Surface Roughness Analysis of Electrodeposited Co Films in an Ionic Liquid Using Electrochemical Surface Plasmon Resonance: Effect of Leveling Additives

Nishi

Ezawa

Sakka

2021

J. Electrochem. Soc.

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“…For the former, the Li UPD/UPS potentials are far negative from the potential of zero charge (PZC), where the EDL structure is in the "crowding" state and the first ionic layer is saturated with cations; therefore, the contribution of the EDL structure is too small and is neglected here. 26,50 For the latter, i.e., the contribution of the diffusion layer, the deposited/stripped Li amount is small with only about monatomic layer thickness, and in contrast, the concentration of Li + in the ILs is high enough to be regarded as constant during the Li UPD/UPS. The time derivative of Δθ SPR can be expressed as…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In addition, Δθ SPR is also generally sensitive enough to the ionic concentration in the EDL ,, and the diffusion layer, , but this is not the case with the present Li UPD/UPS case. For the former, the Li UPD/UPS potentials are far negative from the potential of zero charge (PZC), where the EDL structure is in the “crowding” state and the first ionic layer is saturated with cations; therefore, the contribution of the EDL structure is too small and is neglected here. , For the latter, i.e., the contribution of the diffusion layer, the deposited/stripped Li amount is small with only about monatomic layer thickness, and in contrast, the concentration of Li + in the ILs is high enough to be regarded as constant during the Li UPD/UPS. The time derivative of Δθ SPR can be expressed as where V Li is the molar volume of Li metal, F is the Faraday constant, and i Li is the current density for the Li UPD/UPS processes.…”

Section: Results and Discussionmentioning

confidence: 99%

In Situ Electrochemical Surface Plasmon Resonance Study on Lithium Underpotential Deposition and Stripping in Bis(fluorosulfonyl)amide-Based Ionic Liquids

et al. 2022

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To sensitively detect the electrode surface roughness change in the initial process of the lithium electrodeposition/dissolution processes in ionic liquids (ILs), electrochemical surface plasmon resonance (ESPR) measurements were performed in an in situ manner on a gold electrode in a glyme-Li salt solvate IL, tetraglyme/lithium bis(fluorosulfonyl)amide ([Li(G4)+][FSA–]), and an IL, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)amide ([C4mim+][FSA–]), containing 100 mM Li+[FSA–]. The SPR angle shifts (ΔθSPR) were tracked simultaneously with the repetitively recorded cyclic voltammograms (CVs) of the Li underpotential deposition (UPD)/underpotential stripping (UPS). ΔθSPR increased/decreased in the UPD/UPS processes, sensitively responding to the refractive index change at the IL/electrode interface. The time derivative ΔθSPR curves basically reproduced CVs but were significantly less influenced by residual current, indicating that ESPR was an effective in situ method to track the Li UPD/UPS processes. In [Li(G4)+][FSA–], the shift in ΔθSPR per deposited Li amount did not change as the CV scan was repeated, indicating no change in surface roughness. In contrast, in [C4mim+][FSA–], the same parameter increased with an increase in the scan number, reflecting the increase in surface roughness as confirmed by Fresnel reflectivity simulations. The comparison of ESPR results with the simulations suggests that for both ILs, the surface of the deposited Li layer was smoothened during the period after the Li UPD and before the Li UPS in CVs.

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“…As described in the last paragraph, SPR is sensitive enough to detect the change in the electric double layer structure during the charging/discharging process. [30][31][32][33][34] Figure 11a shows the shift of SPR angle, ¦H (= H SPR ¹ H SPR,0 , where H SPR,0 is H SPR when the measurements are started) during CV measurements within the potential window at the interface between Au thin film and an ionic liquid. 31 The SPR angle changes in a sigmoidal manner, in response to a negative potential sweep, almost independent of the three scan rates.…”

Section: Electric Double Layermentioning

confidence: 99%

Electrochemical In Situ/operando Spectroscopy and Microscopy Part 1: Fundamentals

et al. 2022

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Spectroscopic and microscopic techniques are complementary to electrochemical studies because electrochemical data consists of current, voltage and time, and has no direct information concerning the chemical structure of active species. Hence electrochemical in situ/ operando spectroscopy and microscopy become powerful tools for identification of the electrochemically active species during the electrochemical reactions. The present comprehensive paper provides the fundamental theory, cell design concepts, and measurement tips of various spectroscopic and microscopic techniques. X-ray absorption spectroscopy, infrared spectroscopy, surface plasmon resonance, Raman spectroscopy, confocal microscopy and electron microscopy are covered in the present paper. The introduced cell design becomes the critical part for chemists and materials scientists to start these measurements. Several advanced techniques from recent studies are also introduced.

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Evaluation of static differential capacitance at the [C₄mim⁺][TFSA⁻]/electrode interface using molecular dynamics simulation combined with electrochemical surface plasmon resonance measurements

Abstract: Molecular dynamic (MD) simulations have been performed for 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C4mim+][TFSA−]), an ionic liquid (IL), on a charged graphene electrode to achieve the quantitative analysis of the static differential capacitance...

Cited by 14 publications

References 88 publications

In Situ Surface Roughness Analysis of Electrodeposited Co Films in an Ionic Liquid Using Electrochemical Surface Plasmon Resonance: Effect of Leveling Additives

In Situ Surface Roughness Analysis of Electrodeposited Co Films in an Ionic Liquid Using Electrochemical Surface Plasmon Resonance: Effect of Leveling Additives

In Situ Electrochemical Surface Plasmon Resonance Study on Lithium Underpotential Deposition and Stripping in Bis(fluorosulfonyl)amide-Based Ionic Liquids

Electrochemical In Situ/<i>operando</i> Spectroscopy and Microscopy Part 1: Fundamentals

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