Voltammetric studies of alkali metal reduction on platinum electrodes

Fried, Ilana; Barak, H.

doi:10.1016/0368-1874(71)85065-7

Cited by 14 publications

(6 citation statements)

References 19 publications

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“…In the case of UPD in aqueous solvents, the values of z ad are, in general, nonintegers . In a fortuitous manner, for nonaqueous solvents, when the depositing species are alkali metals, n = z ad is shown to be unity, indicating a complete discharge of the ions. This feature provides considerable simplicity in the analysis.…”

Section: Underpotential Deposition In Nonaqueous Solventsmentioning

confidence: 93%

“…Scheme ). In Table , the calculated UPD shifts for various couples in ACN and PC have been reported, and n is assumed to be unity since the reduction of alkali metals has been shown to undergo a complete one-electron transfer . While the agreement with the experimentally obtained UPD shift is satisfactory, it may be pointed out that the bond dissociation energies, adsorbate sizes, and coordination numbers are somewhat approximate estimates.…”

Section: Underpotential Deposition In Nonaqueous Solventsmentioning

confidence: 95%

“…Since the ratio between the accumulated charge and the corresponding potential dictates the capacitance, eqs 1 and 2 which incorporate different energetic contributions involving the depositing species, solvent dipoles, and the electrode substrate provide a preliminary estimate of the capacitances. The values of C φ for couples such as Au/Li + (ACN), Cu/Li + (PC), Pt/Li + (PC), Pt/Na + (PC), and Pt/Cs + (PC), deduced using q p (from eq 6) and the potential window, , span a range ca. 40−240 μF cm -2 .…”

Section: Perspectives and Summarymentioning

confidence: 99%

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Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents

Sudha

Sangaranarayanan

2003

J. Phys. Chem. B

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The underpotential deposition (UPD) shifts of different metallic couples in acetonitrile and propylene carbonate are estimated using work function differences, lattice coordination numbers, and adsorption energies of solvent dipoles. The bulk deposition arising from monolayer and multilayer formation is considered. A satisfactory agreement of the UPD shift with the experimental data deduced from anodic stripping voltammetry is noticed.Apart from evaluating the surface potential of electrons in metals using the potential of monolayer adsorption and bulk deposition, the significance of the methodology in the development of electrochemical capacitors is indicated.

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Section: Underpotential Deposition In Nonaqueous Solventsmentioning

confidence: 93%

Section: Underpotential Deposition In Nonaqueous Solventsmentioning

confidence: 95%

Section: Perspectives and Summarymentioning

confidence: 99%

See 1 more Smart Citation

Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents

Sudha

Sangaranarayanan

2003

J. Phys. Chem. B

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“…173 The highest observed at present is 1.7 V for on Pt in PC. 174 In aqueous solution, it is 1.4 V for on Pt(111). 129 These large values suggest the possibility of an underpotential deposition supercapacitor or a secondary battery of any combination of in nonaqueous media, as shown in Fig.…”

Section: Underpotential Deposition In Nonaqueous Solventsmentioning

confidence: 99%

Underpotential Deposition on Single-Crystal Metals

Aramata

2002

Modern Aspects of Electrochemistry

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“…In recent years, undervoltage deposition of Li has been reported from organic solvents into a variety of metals at room temperature, e.g., Sn, Pb, A1, Au, Zn, Cd (22), and Pt (22,23). Intermetallic Li compounds were formed.…”

Section: Some Implications Of Undervoltage Deposition O] Alkali Metal...mentioning

confidence: 99%

Undervoltage Deposition of Alkali Metal at Carbon Electrodes in the LiCl ‐ KCl Eutectic Melt

James¹

1975

J. Electrochem. Soc.

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Voltammograms and charge‐discharge curves are presented for carbon electrodes of varying graphitic crystallinity in normalLiCl‐normalKCl eutectic melt at 703°K (430°C). For rods of glassy carbon, graphite, and pyrolytic graphite there is a very marked cathodic depolarization below about −2.5V vs. a chlorine electrode. Chemical analysis of the cathodized carbons shows that this depolarization is caused by undervoltage deposition of alkali metal. The deposited metal normally consists entirely of Li but in two cases, during potentiostatic cathodizing, significant amounts of K were codeposited. Cathodized graphite rods disintegrate before reaching the Li potential but glassy carbon rods do not and can survive about 25 charge‐discharge cycles before breaking up. The uninflected charging curves obtained for glassy carbon and graphite give no indication of distinct transitions between Li intercalation compounds of different stages. However, the relatively low Li contents of cathodized carbons, their x‐ray diffraction patterns and the absence of acetylene in their reaction with water all favor the presence of intercalation compounds rather than a carbide. Lithium contents of glassy carbon rods cathodized toward the Li potential range up to about 7 weight per cent compared with 8.9% for C6normalLi , the richest intercalation compound and 37% for Li2C2 . Even quite brief exposures of carbon electrodes in this melt to potentials below −2.5V have lasting effects on electrode behavior; carbon loses its melt‐repellency and the electrode suffers a 1–2V lowering of its open‐circuit voltage.

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Voltammetric studies of alkali metal reduction on platinum electrodes

Cited by 14 publications

References 19 publications

Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents

Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents

Underpotential Deposition on Single-Crystal Metals

Undervoltage Deposition of Alkali Metal at Carbon Electrodes in the LiCl ‐ KCl Eutectic Melt

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