Electrodeposition of Metals in Ionic Liquids

Katayama, Yasushi

doi:10.1002/9781118003350.ch9

Cited by 13 publications

(12 citation statements)

References 157 publications

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“…One alternative to the use of traditional aqueous baths are room temperature ionic liquids (RTILs). Since RTILs have a wide electrochemical window (3–5 V) and sufficient conductivity, these new solvents are suitable for metal electrodeposition applications, although they show relatively low metal solubility. − Unfortunately, the high cost of RTILs limits bulk applications, and more feasible alternatives are explored. In this context, deep eutectic solvents (DESs) have emerged as the cheaper and greener alternative to RTILs. − DESs share many benefits with RTILs: tunability, sufficient conductivity, similar mass transport properties, and a wider electrochemical window than aqueous electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Surface Sensitive Nickel Electrodeposition in Deep Eutectic Solvent

Sebastián

Giannotti

Gómez

et al. 2018

ACS Appl. Energy Mater.

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The first steps of nickel electrodeposition in a deep eutectic solvent (DES) are analysed in detail. Several substrates from glassy carbon to Pt(111) were investigated pointing out the surface sensitivity of the nucleation and growth mechanism. For that, cyclic voltammetry and chronoamperometry, in combination with scanning electron microscopy (SEM), were employed. X-ray diffraction (XRD) and atomic force microscopy (AFM) were used to more deeply analyse the Ni deposition on Pt substrates.In a 0.1 M NiCl 2 + DES solution (at 70ºC), the nickel deposition on glassy carbon takes place within the potential limits of the electrode in the blank solution. Although, the electrochemical window of Pt|DES is considerably shorter than on glassy carbon|DES, it was still sufficient for the nickel deposition. On Pt electrode, the negative potential limit was enlarged while the nickel deposit growed, likely because of the lower catalytic activity of the nickel towards the reduction of the DES. At lower overpotentials, different hydrogenated Ni structures were favoured, most likely because of the DES co-reduction on the Pt substrate. Nanometric metallic nickel grains of rounded shape were obtained in any substrate, as evidenced by the FE-SEM. Passivation phenomena, related to the formation of Ni oxide and Ni hydroxylated species, were observed at high applied overpotentials. At low deposited charge, on Pt(111) the AFM measurements showed the formation of rounded nanometric particles of Ni, which rearranged and formed small triangular arrays at sufficiently low applied overpotential (Scheme 1). This particle pattern was induced by the <111> orientation and related to surface sensitivity of the nickel deposition in DES. The present work provides deep insights into the Ni electrodeposition mechanism in the selected deep eutectic solvent. Scheme 1. Representation of the Ni(II) electrodeposition in DES on Pt(111) and AFM image (2 x 2 µm 2 ) of the Ni clusters.

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Section: Introductionmentioning

confidence: 99%

Surface Sensitive Nickel Electrodeposition in Deep Eutectic Solvent

Sebastián

Giannotti

Gómez

et al. 2018

ACS Appl. Energy Mater.

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“…Moreover, the electrochemical window of some ILs can be up to 7 V, depending on the chemical nature of the cation and anion. [5][6][7] Hence, the most active field in electrochemistry, together with RTILs, is currently focused on electrodeposition, [8][9][10] supercapacitors, 11 batteries, [12][13][14] and the study of the heterogeneous electron transfer of electroactive organic compounds in RTILs. [15][16][17][18][19][20][21] It is important to note that the ''stabilization'' of radicals and radical anions has been observed in few cases (such as nitroderivatives, 15,16 halogenated compounds, 22,23 acetophenone, 24 stilbene, 25 and superoxide ions 26 ).…”

Section: Introductionmentioning

confidence: 99%

The role of cations in the reduction of 9-fluorenone in bis(trifluoromethylsulfonyl)imide room temperature ionic liquids

2014

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“…Specifically, at mole LA:LB ratios <1, the liquids are termed Lewis basic; at LA:LB ratios = 1, the liquid is termed neutral; and at LA:LB ratios >1, the liquids are termed Lewis acidic. 38,39 Consequently, there is often an ideal mole ratio between the LA and LB that seeks to increase the conductivity (>5 mS cm −1 ) and decrease the viscosity (<50 cP). The Lewis acidity also impacts the electroactive Al species present.…”

Section: ■ Introductionmentioning

confidence: 99%

Measuring and Enhancing the Ionic Conductivity of Chloroaluminate Electrolytes for Al-Ion Batteries

et al. 2023

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At the core of the aluminum (Al) ion battery is the liquid electrolyte, which governs the underlying chemistry. Optimizing the rheological properties of the electrolyte is critical to advance the state of the art. In the present work, the chloroaluminate electrolyte is made by reacting AlCl3 with a recently reported acetamidinium chloride (Acet-Cl) salt in an effort to make a more performant liquid electrolyte. Using AlCl3:Acet-Cl as a model electrolyte, we build on our previous work, which established a new method for extracting the ionic conductivity from fitting voltammetric data, and in this contribution, we validate the method across a range of measurement parameters in addition to highlighting the model electrolytes’ conductivity relative to current chloroaluminate liquids. Specifically, our method allows the extraction of both the ionic conductivity and voltammetric data from a single, simple, and routine measurement. To bring these results in the context of current methods, we compare our results to two independent standard conductivity measurement techniques. Several different measurement parameters (potential scan rate, potential excursion, temperature, and composition) are examined. We find that our novel method can resolve similar trends in conductivity to conventional methods, but typically, the values are a factor of two higher. The values from our method, on the other hand, agree closely with literature values reported elsewhere. Importantly, having now established the approach for our new method, we discuss the conductivity of AlCl3:Acet-Cl-based formulations. These electrolytes provide a significant improvement (5–10× higher) over electrolytes made from similar Lewis base salts (e.g., urea or acetamide). The Lewis base salt precursors have a low economic cost compared to state-of-the-art imidazolium-based salts and are non-toxic, which is advantageous for scale-up. Overall, this is a noteworthy step at designing cost-effective and performant liquid electrolytes for Al-ion battery applications.

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Electrodeposition of Metals in Ionic Liquids

Cited by 13 publications

References 157 publications

Surface Sensitive Nickel Electrodeposition in Deep Eutectic Solvent

Surface Sensitive Nickel Electrodeposition in Deep Eutectic Solvent

The role of cations in the reduction of 9-fluorenone in bis(trifluoromethylsulfonyl)imide room temperature ionic liquids

Measuring and Enhancing the Ionic Conductivity of Chloroaluminate Electrolytes for Al-Ion Batteries

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