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Barthel, J.; Neueder, Roland; Poepke, Herbert; Wittmann, Harald

doi:10.1023/a:1022674613995

Cited by 26 publications

(24 citation statements)

References 14 publications

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“…Based on the measurements by Scholl and Sochaj on the ferrocene/ferrocenium couple on a gold electrode in acetonitrile (D R = 2.43 · 10 −5 cm 2 /s, D O = 2.31 · 10 −5 cm 2 /s, k 0 = 0.088 cm/s), Eq. 22 would yield a value of = 11.6, which indeed is reasonably consistent with the peak separation of ∼63 mV at ≥5 mM LiClO 4 shown in Figure 5. 20 For LiClO 4 concentrations below 5 mM (at a ferrocene concentration of 0.05 mM), the observed increase in peak separation may be due to several effects and is currently not understood.…”

Section: Resultssupporting

confidence: 84%

“…For example, a decrease in peak separation of ∼2 mV is expected for a 1 mM LiClO 4 concentration, if the concentration overpotential is subtracted from the oxidation peak potential. This low value is a result of the chosen experimental setup with a minimal ferrocene to LiClO 4 concentration ratio (1/20 at 1 mM LiClO 4 ). An obvious trend is only visible for the smallest LiClO 4 concentration of 0.1 mM LiClO 4 , where the half peak potential is clearly shifted towards the oxidation peak as a result of the non-symmetric behavior of the concentration overpotential as explained in the Theory section.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction Gibbs energy R G for the lithium reaction at the RE is given by R G| RE = 0 = μ Li −μ Li + −μ e − [4] and for the ferrocene reaction at the WE by…”

Section: LImentioning

confidence: 99%

“…If the ferrocene concentration is kept constant for different LiClO 4 concentrations, U Ref can be shown to be constant as will be discussed in detail in section Reference potential. In summary, the relation given in Eq.…”

Section: LImentioning

confidence: 99%

See 3 more Smart Citations

Direct Electrochemical Determination of Thermodynamic Factors in Aprotic Binary Electrolytes

Landesfeind¹,

Ehrl²,

Graf³

et al. 2016

J. Electrochem. Soc.

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We propose a novel method to determine the thermodynamic factor of binary salts dissolved in aprotic solvents as a function of salt concentration. The method is based on cyclic voltammetry experiments conducted in a three-electrode cell with the ferrocene/ferrocenium redox couple being used as an internal standard. The main advantage of this experimental setup is the direct electrochemical determination of the thermodynamic factor from a single type of experiment without the necessity of additional assumptions on other transport parameters. The theoretical derivation of the used relationship between peak/half-wave potentials and the thermodynamic factor as well as non-ideal effects which distort the experimental results, such as uncompensated resistances or concentration overpotentials are discussed in detail. Different strategies are suggested to avoid these non-ideal effects using the peak separation of the cyclic voltammograms as an inherent quality measure for the experimental data. Applicability of the experimental procedure is demonstrated for LiClO 4 in EC:DEC (1:1, w:w) in the range from 5 mM to 2 M and repeated for typical LiPF 6 containing electrolytes. At the end, the obtained results are compared to thermodynamic factors of similar electrolyte solutions published in literature.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

“…The reaction Gibbs energy R G for the lithium reaction at the RE is given by R G| RE = 0 = μ Li −μ Li + −μ e − [4] and for the ferrocene reaction at the WE by…”

Section: LImentioning

confidence: 99%

Section: LImentioning

confidence: 99%

See 2 more Smart Citations

Direct Electrochemical Determination of Thermodynamic Factors in Aprotic Binary Electrolytes

Landesfeind¹,

Ehrl²,

Graf³

et al. 2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…[36] Over the past decade, DFT and ab initio calculations on [Li(CH 3 CN) n ] + and related clusters were also performed by different groups. [30,[37][38][39][40] There has been a special interest in the properties of Li salts, such as conductivity, [41][42][43][44] transport abililty, [45][46][47] viscosity, [48] and osmotic behaviour [49] , in solvents and solvent mixtures because of the use of Li + ions in batteries of high energy density. [50] Such studies are not restricted to liquid systems.…”

Section: Introductionmentioning

confidence: 99%