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.

NMR analysis of phosphoric acid distribution in porous fuel cell catalysts.

Understanding the interaction of phosphoric acid and porous electrocatalysts is of vital importance for a rational design of high performance phosphoric acid based fuel cells on a molecular level. We demonstrate for the first time that NMR spectroscopy can be used for elucidating the preferred distribution sites of phosphoric acid in various nanoporous carbons. A pore size dependent negative chemical shift of 31P is observed, serving as a distinct signature of pore occupation, and applied for analysing a commercial catalyst (Pt@Vulcan) as a practical application.

Degradation Characteristics of Electrospun Gas Diffusion Layers with Custom Pore Structures for Polymer Electrolyte Membrane Fuel Cells.

Electrospinning has been demonstrated to be a versatile technique for producing hydrophobic gas diffusion layers (GDLs) with customized pore structures for the enhanced performance of polymer electrolyte membrane (PEM) fuel cells. However, the degradation characteristics of custom hydrophobic electrospun GDLs (eGDLs) have not yet been explored. Here, for the first time, we investigate the degradation characteristics of custom hydrophobic eGDLs via an ex situ accelerated degradation protocol using H2O2. The surface contact angle of degraded eGDLs (44 ± 12°) was lower than that of pristine eGDLs (137 ± 6°). The loss of hydrophobicity was attributed to the degradation (via hydrolysis) of the fluorinated monolayers (formed via a direct fluorination treatment) on the electrospun carbon fiber surfaces as evidenced by the reduction in surface fluorine content. Degradation of the surface monolayers affected fuel cell performance under multiple operating conditions. At 100% relative humidity (RH), the loss of monolayers led to higher liquid water content and lower cell voltages compared to the pristine eGDL. At 50% RH, the degraded eGDL led to lower cell voltages due to the lower electrical conductivity of the degraded materials. The lower electrical conductivity was attributed to the oxidation of carbon fibers upon loss of the monolayers. Our results indicate the importance of designing robust hydrophobic surface treatments for the advancement of customized GDLs for effective long-term fuel cell operation.

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.

Porous N- and S-doped carbon-carbon composite electrodes by soft-templating for redox flow batteries.

Highly porous carbon-carbon composite electrodes for the implementation in redox flow battery systems have been synthesized by a novel soft-templating approach. A PAN-based carbon felt was embedded into a solution containing a phenolic resin, a nitrogen source (pyrrole-2-carboxaldehyde) and a sulfur source (2-thiophenecarboxaldehyde), as well as a triblock copolymer (Pluronic® F-127) acting as the structure-directing agent. By this strategy, highly porous carbon phase co-doped with nitrogen and sulfur was obtained inside the macroporous carbon felt. For the investigation of electrode structure and porosity X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and nitrogen sorption (BET) were used. The electrochemical performance of the carbon felts was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The N- and S-doped carbon electrodes show promising activity for the positive side reaction and could be seen as a significant advance in the design of carbon felt electrodes for use in redox flow batteries.

Materials and characterization techniques for high-temperature polymer electrolyte membrane fuel cells.

The performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) is critically dependent on the selection of materials and optimization of individual components. A conventional high-temperature membrane electrode assembly (HT-MEA) primarily consists of a polybenzimidazole (PBI)-type membrane containing phosphoric acid and two gas diffusion electrodes (GDE), the anode and the cathode, attached to the two surfaces of the membrane. This review article provides a survey on the materials implemented in state-of-the-art HT-MEAs. These materials must meet extremely demanding requirements because of the severe operating conditions of HT-PEMFCs. They need to be electrochemically and thermally stable in highly acidic environment. The polymer membranes should exhibit high proton conductivity in low-hydration and even anhydrous states. Of special concern for phosphoric-acid-doped PBI-type membranes is the acid loss and management during operation. The slow oxygen reduction reaction in HT-PEMFCs remains a challenge. Phosphoric acid tends to adsorb onto the surface of the platinum catalyst and therefore hampers the reaction kinetics. Additionally, the binder material plays a key role in regulating the hydrophobicity and hydrophilicity of the catalyst layer. Subsequently, the binder controls the electrode-membrane interface that establishes the triple phase boundary between proton conductive electrolyte, electron conductive catalyst, and reactant gases. Moreover, the elevated operating temperatures promote carbon corrosion and therefore degrade the integrity of the catalyst support. These are only some examples how materials properties affect the stability and performance of HT-PEMFCs. For this reason, materials characterization techniques for HT-PEMFCs, either in situ or ex situ, are highly beneficial. Significant progress has recently been made in this field, which enables us to gain a better understanding of underlying processes occurring during fuel cell operation. Various novel tools for characterizing and diagnosing HT-PEMFCs and key components are presented in this review, including FTIR and Raman spectroscopy, confocal Raman microscopy, synchrotron X-ray imaging, X-ray microtomography, and atomic force microscopy.

Organization of acenes with a cruciform assembly motif.

This study explores the assembly in the crystalline state of a class of pentacenes that are substituted along their long edges with aromatic rings forming rigid, cruciform molecules. The crystals were grown from the gas phase, and their structures were compared with DFT-optimized geometries. Both crystallographic and computed structures show that a planar acene core is the exception rather than the rule. In the assembly of these molecules, the phenyl groups block the herringbone motif and further guide the arrangement of the acene core into higher order structures. The packing for the phenyl-substituted derivatives is dictated by close contacts between the C-H's of the pendant aromatic rings and the carbons at the fusions in the acene backbone. Using thiophene substituents instead of phenyls creates cofacially stacked acenes. In thin films, the thiophene-substituted derivative forms devices with good electrical properties: relatively high mobility, high ON/OFF ratios, and low threshold voltage for device activation. An unusual result is obtained for the decaphenyl pentacene when devices are fabricated on its crystalline surface. Although its acene cores are well isolated from each other, this material still exhibits good electrical properties.

Pentacene disproportionation during sublimation for field-effect transistors.

At moderate temperatures in flowing gas, pentacene undergoes a disproportionation reaction to produce 6,13-dihydropentacene (DHP) and a series of polycondensed aromatic hydrocarbons, including the previously unknown peripentacene (PP). The process requires activation by heating to 320 degrees C and is possibly catalyzed by impurities such as DHP, 6,13-pentacenequinone (PQ), Al, or Fe found in the starting materials. These impurities also result in a decrease in the intrinsic field-effect mobility (FEM) of pentacene crystals. Subsequent purifications remove such impurities, thus inhibiting the formation of the disproportionation products and increasing the FEM of pentacene (2.2 cm(2)/Vs). These results clarify the importance of purification of semiconductive materials for measurements of intrinsic mobility and optimal device performance.

Synthesis, crystal structure, and transistor performance of tetracene derivatives.

The substitution of chloro or bromo groups in tetracene gives rise to the change of crystal structure, having a substantial effect on carrier transport. Halogenated tetracene derivatives were synthesized and grown into single crystals. Monosubstituted 5-bromo- and 5-chlorotetracenes have the herringbone-type structure, while 5,11-dichlorotetracene has the slipped pi stacking structure. Mobility of 5,11-dichlorotetracene was measured to be as high as 1.6 cm2/V.s in single-crystal transistors. The pi stacking structure, which enhances pi orbital overlap and facilitates carrier transport, may thus be responsible for this high mobility.