Verification and Analysis of Transference Number Measurements by the Galvanostatic Polarization Method

Abstract

Measurements of the Ag ϩ transference numbers in 0.1025 and 1.010 M aqueous silver nitrate solutions were used to verify the accuracy of the galvanostatic polarization method for transference number determinations in concentrated solutions of binary electrolytes. Simulations were performed to analyze the experimental data and sources of error. Experimental results were within 4% of literature values at 0.1025 M and within 9% at 1.010 M, the latter presumably due to a deviation from the method's assumption of a convection-free system. The method should be immune to convection when used in polymer electrolytes (for which it was originally developed) and is expected to be accurate to 4% or better in such systems. Three improvements, i.e., a new extrapolation method, a refined fitting procedure, and a means of identifying problematic runs have also been incorporated into the galvanostatic polarization method and are described.

Transport Properties of LiPF[sub 6]-Based Li-Ion Battery Electrolytes

“…Diffusion coefficients were extracted using the galvanostatic polarization method 30 using the E-One Moli Energy charger system. Custom-designed cylindrical cells of 100 mm length and diameters ranging from 5 to 20 mm were used for the measurements.…”

Electrochemical characterization of electrolytes for lithium-ion batteries based on lithium difluoromono(oxalato)borate

“…For the determination of transference numbers, three different measurements are combined: measurement of the potential during galvanostatic polarization, determination of the salt diffusion coefficient, and evaluation of concentration dependence of the cell potential. With these parameters the cationic transference number can be calculated by [30]:…”

A Theoretical and Experimental Study of the Mass Transport in Gel Electrolytes I. Mathematical Analysis of Characterization Method

“…An expression for the build-up of the diffusion potential is not presented here since it contains the same parameters as the relaxation and thus contains no unique information about the mass transport. The expression for the relaxation can be compared to the one reported by Hafezi et al 11 for a liquid electrolyte, which was derived for semi-infinite conditions. Their expression indicates that a plot of the relaxation potential against a transformed time variable should be a straight line through the origin.…”