Abstract
Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2+. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2+ inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.
Highlights
Due to their theoretically unlimited capacity and their long life cycle, redox flow batteries (RFB) are promising candidates for short- and long-term energy storage of wind, water and solar power
The vanadium redox flow battery (VRFB) consists of two half-cells separated by a polymer electrolyte membrane (PEM)
The experimental design needed to optimize for (i) minimized alteration of the vanadium species, (ii) spatial resolution sufficient to resolve the profile of the vanadium species, (iii) sufficient statistics and (iv) minimized vanadium diffusion
Summary
Due to their theoretically unlimited capacity and their long life cycle, redox flow batteries (RFB) are promising candidates for short- and long-term energy storage of wind, water and solar power. Mesu et al (2007) studied the influence of X-ray irradiation (photon flux density 1.7 Â 1014 photons sÀ1 mmÀ2) on organic copper complexes in aqueous solution during XANES analysis According to their results, the copper changed oxidation state from 2+ to 0 due to water radiolysis. A diffusion cell was constructed which allowed through-plane diffusion from two sides as well as efficient cooling by the Oxford Cryostream With this cell, profiles of the vanadium species in Nafion 117 membranes could be obtained with a resolution of 2.5 mm. The results show that redox reactions inside Nafion take place during through-plane diffusion These procedures could perhaps be adapted for the investigation of other ionomeric membranes or X-ray sensitive samples.
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