We report on single-electrode electrochemical impedance spectroscopy studies of an all-vanadium redox battery using a dynamic hydrogen reference electrode. The negative electrode, comprising the V 2+ /V 3+ couple, contributes approximately 80% of the total cell overpotential during discharge. The impedance spectra measured at the negative electrode exhibit high-frequency, semicircular arcs which correspond to the double layer capacitance in parallel with a faradaic resistance. The faradaic resistance decreases in magnitude with increasing polarization. Integration of the current-dependent faradaic resistance quantifies the fraction of the overvoltage that is attributed to the kinetic limitations of the charge transfer reaction.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 160.36.178.25 Downloaded on 2015-01-08 to IP

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An improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the ratelimiting processes for the V 2+ /V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmic resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.

We present an in situ electrochemical technique for the quantitative measurement and resolution of the ohmic, charge transfer and diffusion overvoltages at the negative electrode of an all-vanadium redox flow battery (VRFB) using electrochemical impedance spectroscopy (EIS). The mathematics describing the complex impedance of the V +2 /V +3 redox reaction is derived and matches the experimental data. The voltage losses contributed by each process have been resolved and quantified at various flow rates and electrode thicknesses as a function of current density during anodic and cathodic polarization. The diffusion overvoltage was affected strongly by flow rate while the charge transfer and ohmic losses were invariant. On the other hand, adopting a thicker electrode significantly changed both the charge transfer and diffusion losses due to increased surface area. Furthermore, the Tafel plot obtained from the impedance resolved charge transfer overvoltage yielded the geometric exchange current density, anodic and cathodic Tafel slopes (135 ± 5 and 121 ± 5 mV/decade respectively) and corresponding transfer coefficients α = 0.45 ± 0.02 and β = 0.50 ± 0.02 in an operating cell.

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