Investigating the V(IV)/V(V) electrode reaction in a vanadium redox flow battery – A distribution of relaxation times analysis

Due to the worldwide increasing energy demand and the urgency to act due to climate change, new energy storage technologies are required to balance the intermittent power supply of renewable energy sources. While the vanadium redox flow battery (VRFB) must still overcome lifetime and efficiency challenges, the technology is a promising candidate for large-scale energy storage. Thus, conducting experiments in a setup that closely mimics the operating conditions is vital for gaining new insights into the reactions and transport processes in a VRFB. We developed a novel 3D printed flow cell to study the individual half cell reactions of a VRFB under precisely controlled operating conditions. Using electrochemical impedance spectroscopy combined with the distribution of relaxation times analysis, we could identify the processes occurring in the half cell with the V(IV)/V(V) redox reaction by varying experimental parameters. We assigned peaks in different frequency ranges to the electrochemical reaction, the transport processes through the porous electrode structure, and the ion transport. This information is essential in the search for optimized operating conditions to improve the VRFB efficiency

Synchrotron X-Ray radiography of vanadium redox flow batteries – Time and spatial resolved electrolyte flow in porous carbon electrodes

A porous carbon electrode fully saturated with electrolyte is one crucial aspect of vanadium redox flow battery efficiency. It determines the electrochemically active surface area, provides more active sites for the reaction during operation, and prevents local degradation due to inhomogeneities in electrolyte distribution. We investigate the electrolyte invasion and distribution at open-circuit potential in heat-treated carbon felt electrodes at varying compression ratios and flow field configurations, using synchrotron X-ray radiography. The quantitative analysis yields time-resolved saturation values of the injection and resolves local changes in saturation to detect areas of lower electrolyte accessibility. Compression ratios of 50% and above lead to a high electrode utilization with more than 97% saturation over the felt thickness. In contrast, carbon felts at 25% and 17% compression only reach 49% and 15% saturation near the flow fields. However, increasing the flow velocity after the injection causes the boundary area next to the flow field to fill even at low compressions. This area is especially critical for the electrode utilization since it is invaded after the bulk. Depending on the compression level, it does not reach full saturation

Revealing the Multifaceted Impacts of Electrode Modifications for Vanadium Redox Flow Battery Electrodes

Carbon electrodes are one of the key components of vanadium redox flow batteries (VRFBs), and their wetting behavior, electrochemical performance, and tendency to side reactions are crucial for cell efficiency. Herein, we demonstrate three different types of electrode modifications: poly(o-toluidine) (POT), Vulcan XC 72R, and an iron-doped carbon–nitrogen base material (Fe–N–C + carbon nanotube (CNT)). By combining synchrotron X-ray imaging with traditional characterization approaches, we give thorough insights into changes caused by each modification in terms of the electrochemical performance in both half-cell reactions, wettability and permeability, and tendency toward the hydrogen evolution side reaction. The limiting performance of POT and Vulcan XC 72R could mainly be ascribed to hindered electrolyte transport through the electrode. Fe–N–C + CNT displayed promising potential in the positive half-cell with improved electrochemical performance and wetting behavior but catalyzed the hydrogen evolution side reaction in the negative half-cell

A Study in Red: The Overlooked Role of Azo‐Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption

The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430–450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H₂ evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies

Revealing the Multifaceted Impacts of Electrode Modifications for Vanadium Redox Flow Battery Electrodes.

Carbon electrodes are one of the key components of vanadium redox flow batteries (VRFBs), and their wetting behavior, electrochemical performance, and tendency to side reactions are crucial for cell efficiency. Herein, we demonstrate three different types of electrode modifications: poly(o-toluidine) (POT), Vulcan XC 72R, and an iron-doped carbon-nitrogen base material (Fe-N-C + carbon nanotube (CNT)). By combining synchrotron X-ray imaging with traditional characterization approaches, we give thorough insights into changes caused by each modification in terms of the electrochemical performance in both half-cell reactions, wettability and permeability, and tendency toward the hydrogen evolution side reaction. The limiting performance of POT and Vulcan XC 72R could mainly be ascribed to hindered electrolyte transport through the electrode. Fe-N-C + CNT displayed promising potential in the positive half-cell with improved electrochemical performance and wetting behavior but catalyzed the hydrogen evolution side reaction in the negative half-cell