Capacity loss induced by the undesired transport of vanadium ions across the ion-exchange membrane (i.e. crossover) is one of the most critical issues associated with vanadium redox flow batteries. This work reports on the manufacturing and testing of an innovative barrier layer to mitigate crossover. The barrier layer conceptual design is described in detail in the patent application WO 2019/197917. The barrier was deposited directly onto Nafion® 212 using the Reactive Spray Deposition Technology, in which carbon-rich particles (∼4–10 nm in diameter) formed in the flame were deposited simultaneously with a mixture of 1100EW Nafion® and Vulcan® XC-72R (∼40 nm diameter) that was sprayed from air-assisted secondary nozzles. During cycles at fixed capacity, the presence of the barrier layer significantly reduced battery self-discharge; the average variation of battery state of charge compared to a reference cell with Nafion® 115 was reduced from 21% to 7%. Moreover, battery energy efficiency was increased by nearly 5%, indicating that the barrier layer does not significantly hinder proton transport. During cycles at 50 mA cm⁻² with fixed cut-off voltages, the barrier layer exhibited stable operation, maintaining a coulombic efficiency around 99.4%. Additionally, the use of the barrier layer projects to a 30% reduction of stack-specific cost.

In vanadium redox flow batteries, the flow field geometry plays a dramatic role on the distribution of the electrolyte and its design results from the trade-off between high battery performance and low pressure drops. In the literature, it was demonstrated that electrolyte permeation through the porous electrode is mainly regulated by pressure difference between adjacent channels, leading to the presence of under-the-rib fluxes. With the support of a 3D computational fluid dynamic model, this work presents two novel flow field geometries that are designed to tune the direction of the pressure gradients between channels in order to promote the under-the-rib fluxes mechanism. The first geometry is named Two Outlets and exploits the splitting of the electrolyte flow into two adjacent interdigitated layouts with the aim to give to the pressure gradient a more transverse direction with respect to the channels, raising the intensity of under-the-rib fluxes and making their distribution more uniform throughout the electrode area. The second geometry is named Four Inlets and presents four inlets located at the corners of the distributor, with an interdigitated-like layout radially oriented from each inlet to one single central outlet, with the concept of reducing the heterogeneity of the flow velocity within the electrode. Subsequently, flow fields performance is verified experimentally adopting a segmented hardware in symmetric cell configuration with positive electrolyte, which permits the measurement of local current distribution and local electrochemical impedance spectroscopy. Compared to a conventional interdigitated geometry, both the developed configurations permit a significant decrease in the pressure drops without any reduction in battery performance. In the Four Inlets flow field the pressure drop reduction is more evident (up to 50%) due to the lower electrolyte velocities in the feeding channels, while the Two Outlets configuration guarantees a more homogeneous current density distribution.