Investigating the Influence of Treatments on Carbon Felts for Vanadium Redox Flow Batteries.

Vanadium redox flow battery (VRFB) electrodes face challenges related to their long-term operation. We investigated different electrode treatments mimicking the aging processes during operation, including thermal activation, aging, soaking, and storing. Several characterization techniques were used to deepen the understanding of the treatment of carbon felts. Synchrotron X-ray imaging, electrochemical impedance spectroscopy (EIS) with the distribution of relaxation times analysis, and dynamic vapor sorption (DVS) revealed differences between the wettability of felts. The bulk saturation after electrolyte injection into the carbon felts significantly differed from 8 % to 96 %. DVS revealed differences in the sorption/desorption behavior of carbon felt ranging from a slight change of 0.8 wt % to over 100 wt %. Additionally, the interactions between the water vapor and the sample change from type V to type H2. After treatment, morphology changes were observed by atomic force microscopy and scanning electron microscopy. Cyclic voltammetry and EIS were used to probe the electrochemical performance, revealing different catalytic activities and transport-related impedances for the treated samples. These investigations are crucial for understanding the effects of treatments on the performance and optimizing materials for long-term operation.

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.

Synchrotron X-ray Radiography and Tomography of Vanadium Redox Flow Batteries-Cell Design, Electrolyte Flow Geometry, and Gas Bubble Formation.

The wetting behavior and affinity to side reactions of carbon-based electrodes in vanadium redox flow batteries (VRFBs) are highly dependent on the physical and chemical surface structures of the material, as well as on the cell design itself. To investigate these properties, a new cell design was proposed to facilitate synchrotron X-ray imaging. Three different flow geometries were studied to understand the impact on the flow dynamics, and the formation of hydrogen bubbles. By electrolyte injection experiments, it was shown that the maximum saturation of carbon felt was achieved by a flat flow field after the first injection and by a serpentine flow field after continuous flow. Furthermore, the average saturation of the carbon felt was correlated to the cyclic voltammetry current response, and the hydrogen gas evolution was visualized in 3D by X-ray tomography. The capabilities of this cell design and experiments were outlined, which are essential for the evaluation and optimization of cell components of VRFBs.