Aqueous Redox Flow Cells Utilizing Verdazyl Cations enabled by Polybenzimidazole Membranes.

Non-aqueous organic redox flow batteries (RFB) utilizing verdazyl radicals are increasingly explored as energy storage technology. Verdazyl cations in RFBs with acidic aqueous electrolytes, however, have not been investigated yet. To advance the application in aqueous RFBs it is crucial to examine the interaction with the utilized membranes. Herein, the interactions between the 1,3,5-triphenylverdazyl cation and commercial Nafion 211 and self-casted polybenzimidazole (PBI) membranes are systematically investigated to improve the performance in RFBs. The impact of polymer backbones is studied by using mPBI and OPBI as well as different pre-treatments with KOH and H3PO4. Nafion 211 shows substantial absorption of the 1,3,5-triphenylverdazylium cation resulting in loss of conductivity. In contrast, mPBI and OPBI are chemically stable against the verdazylium cation without noticeable absorption. Pre-treatment with KOH leads to a significant increase in ionic conductivity as well as low absorption and permeation of the verdazylium cation. Symmetrical RFB cell tests on lab-scale highlight the beneficial impact of PBI membranes in terms of capacity retention and I-V curves over Nafion 211. With only 2% d-1 capacity fading 1,3,5-triphenylverdazyl cations in acidic electrolytes with low-cost PBI based membranes exhibit a higher cycling stability compared to state-of-the-art batteries using verdazyl derivatives in non-aqueous electrolytes.

Microporous Electrode Binders for Anion Exchange Membrane Water Electrolyzers.

In anion exchange membrane (AEM) water electrolyzers, AEMs separate hydrogen and oxygen, but should efficiently transport hydroxide ions. In the electrodes, catalyst nanoparticles are mechanically bonded to the porous transport layer or membrane by a polymeric binder. Since these binders form a thin layer on the catalyst particles, they should not only transport hydroxide ions and water to the catalyst particles, but should also transport the nascating gases away. In the worst case, if formation of gases is >> than gas transport, a gas pocket between catalyst surface and the binder may form and hinder access to reactants (hydroxide ions, water). In this work, the ion conductive binder SEBS-DABCO is blended with PIM-1, a highly permeable polymer of intrinsic microporosity. With increasing amount of PIM-1 in the blends, the permeability for water (selected to represent small molecules) increases. Simultaneously, swelling and conductivity decrease, due to the increased hydrophobicity. Ex situ data and electrochemical data indicate that blends with 50% PIM-1 have better properties than blends with 25% or 75% PIM-1, and tests in the electrolyzer confirm an improved performance when the SEBS-DABCO binder contains 50% PIM-1.

Separators and Membranes for Advanced Alkaline Water Electrolysis.

Traditionally, alkaline water electrolysis (AWE) uses diaphragms to separate anode and cathode and is operated with 5-7 M KOH feed solutions. The ban of asbestos diaphragms led to the development of polymeric diaphragms, which are now the state of the art material. A promising alternative is the ion solvating membrane. Recent developments show that high conductivities can also be obtained in 1 M KOH. A third technology is based on anion exchange membranes (AEM); because these systems use 0-1 M KOH feed solutions to balance the trade-off between conductivity and the AEM's lifetime in alkaline environment, it makes sense to treat them separately as AEM WE. However, the lifetime of AEM increased strongly over the last 10 years, and some electrode-related issues like oxidation of the ionomer binder at the anode can be mitigated by using KOH feed solutions. Therefore, AWE and AEM WE may get more similar in the future, and this review focuses on the developments in polymeric diaphragms, ion solvating membranes, and AEM.

Aryl ether-free polymer electrolytes for electrochemical and energy devices.

Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis via nucleophilic substitution, alkylation of polybenzimidazole, and Diels-Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure-property-performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO2 electrolysers, along with the current status of scale-up synthesis and commercialization.

Electrode Separators for the Next-Generation Alkaline Water Electrolyzers.

Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw materials. Even though it is a mature technology, the new technological context of the renewable energy system demands more from the systems in terms of higher energy efficiency, enhanced rate capability, as well as dynamic, part-load, and differential pressure operation capability. New electrode separators that can support high currents at small ohmic losses, while effectively suppressing gas crossover, are essential to achieving this. This Focus Review compares the three main development paths that are currently being pursued in the field with the aim to identify the advantages and drawbacks of the different approaches in order to illuminate rational ways forward.

Membrane Assemblies with Soft Protective Layers: Dense and Gel-Type Polybenzimidazole Membranes and Their Use in Vanadium Redox Flow Batteries.

Polybenzimidazole (PBI) membranes show excellent chemical stability and low vanadium crossover in vanadium redox flow batteries (VRFBs), but their high resistance is challenging. This work introduces a concept, membrane assemblies of a highly selective 2 µm thin PBI membrane between two 60 µm thick highly conductive PBI gel membranes, which act as soft protective layers against external mechanical forces and astray carbon fibers from the electrode. The soft layers are produced by casting phosphoric acid solutions of commercial PBI powder into membranes and exchanging the absorbed acid into sulfuric acid. A conductivity of 565 mS cm-1 is achieved. A stability test indicates that gel mPBI and dense PBI-OO have higher stability than dense mPBI and dense py-PBI, and gel/PBI-OO/gel is successfully tested for 1070 cycles (ca. 1000 h) at 100 mA cm-2 in the VRFB. The initial energy efficiency (EE) for the first 50 cycles is 90.5 ± 0.2%, and after a power outage stabilized at 86.3 ± 0.5% for the following 500 cycles. The initial EE is one of the highest published so far, and the materials cost for a membrane assembly is 12.35 U.S. dollars at a production volume of 5000 m2 , which makes these membranes very attractive for commercialization.

Properties of Anion Exchange Membranes with a Focus on Water Electrolysis.

Recently, alkaline membrane water electrolysis, in which membranes are in direct contact with water or alkaline solutions, has gained attention. This necessitates new approaches to membrane characterization. We show how the mechanical properties of FAA3, PiperION, Nafion 212 and reinforced FAA3-PK-75 and PiperION PI-15 change when stress−strain curves are measured in temperature-controlled water. Since membranes show dimensional changes when the temperature changes and, therefore, may experience stresses in the application, we investigated seven different membrane types to determine if they follow the expected spring-like behavior or show hysteresis. By using a very simple setup which can be implemented in most laboratories, we measured the "true hydroxide conductivity" of membranes in temperature-controlled water and found that PI-15 and mTPN had higher conductivity at 60 °C than Nafion 212. The same setup was used to monitor the alkaline stability of membranes, and it was found that stability decreased in the order mTPN > PiperION > FAA3. XPS analysis showed that FAA3 was degraded by the attack of hydroxide ions on the benzylic position. Water permeability was analyzed, and mTPN had approximately two times higher permeability than PiperION and 50% higher permeability than FAA3.

Synthesis of Sulfonated Poly(Arylene Ether Sulfone)s Containing Aliphatic Moieties for Effective Membrane Electrode Assembly Fabrication by Low-Temperature Decal Transfer Methods.

The purpose of this study was to investigate the effect of the aliphatic moiety in the sulfonated poly(arylene ether sulfone) (SPAES) backbone. A new monomer (4,4'-dihydroxy-1,6-diphenoxyhexane) was synthesized and polymerized with other monomers to obtain partially alkylated SPAESs. According to differential scanning calorimetry analysis, the glass transition temperature (Tg) of these polymers ranged from 85 to 90 °C, which is 100 °C lower than that of the fully aromatic SPAES. Due to the low Tg values obtained for the partially alkylated SPAESs, it was possible to prepare a hydrocarbon electrolyte membrane-based membrane electrode assembly (MEA) with Nafion® binder in the electrode through the use of a decal transfer method, which is the most commercially suitable system to obtain an MEA of proton exchange membrane fuel cells (PEMFCs). A single cell prepared using this partially alkylated SPAES as an electrolyte membrane exhibited a peak power density of 539 mW cm-2.

Polystyrene-Based Hydroxide-Ion-Conducting Ionomer: Binder Characteristics and Performance in Anion-Exchange Membrane Fuel Cells.

Polystyrene-based polymers with variable molecular weights are prepared by radical polymerization of styrene. Polystyrene is grafted with bromo-alkyl chains of different lengths through Friedel-Crafts acylation and quaternized to afford a series of hydroxide-ion-conducting ionomers for the catalyst binder for the membrane electrode assembly in anion-exchange membrane fuel cells (AEMFCs). Structural analyses reveal that the molecular weight of the polystyrene backbone ranges from 10,000 to 63,000 g mol-1, while the ion exchange capacity of quaternary-ammonium-group-bearing ionomers ranges from 1.44 to 1.74 mmol g-1. The performance of AEMFCs constructed using the prepared electrode ionomers is affected by several ionomer properties, and a maximal power density of 407 mW cm-2 and a durability exceeding that of a reference cell with a commercially available ionomer are achieved under optimal conditions. Thus, the developed approach is concluded to be well suited for the fabrication of next-generation electrode ionomers for high-performance AEMFCs.

Vanadium Redox Flow Batteries Using meta-Polybenzimidazole-Based Membranes of Different Thicknesses.

15, 25, and 35 µm thick meta-polybenzimidazole (PBI) membranes are doped with H2SO4 and tested in a vanadium redox flow battery (VRFB). Their performances are compared with those of Nafion membranes. Immersed in 2 M H2SO4, PBI absorbs about 2 mol of H2SO4 per mole of repeat unit. This results in low conductivity and low voltage efficiency (VE). In ex-situ tests, meta-PBI shows a negligible crossover of V3+ and V4+ ions, much lower than that of Nafion. This is due to electrostatic repulsive forces between vanadium cations and positively charged protonated PBI backbones, and the molecular sieving effect of PBI's nanosized pores. It turns out that charge efficiency (CE) of VRFBs using meta-PBI-based membranes is unaffected by or slightly increases with decreasing membrane thickness. Thick meta-PBI membranes require about 100 mV larger potentials to achieve the same charging current as thin meta-PBI membranes. This additional potential may increase side reactions or enable more vanadium ions to overcome the electrostatic energy barrier and to enter the membrane. On this basis, H2SO4-doped meta-PBI membranes should be thin to achieve high VE and CE. The energy efficiency of 15 µm thick PBI reaches 92%, exceeding that of Nafion 212 and 117 (N212 and N117) at 40 mA cm-2.

Transition metal alloying effect on the phosphoric acid adsorption strength of Pt nanoparticles: an experimental and density functional theory study.

The effect of alloying with transition metals (Ni, Co, Fe) on the adsorption strength of phosphoric acid on Pt alloy surfaces was investigated using electrochemical analysis and first-principles calculations. Cyclic voltammograms of carbon-supported Pt3M/C (M = Ni, Co, and Fe) electrocatalysts in 0.1 M HClO4 with and without 0.01 M H3PO4 revealed that the phosphoric acid adsorption charge density near the onset potential on the nanoparticle surfaces was decreased by alloying with transition metals in the order Co, Fe, Ni. First-principles calculations based on density functional theory confirmed that the adsorption strength of phosphoric acid was weakened by alloying with transition metals, in the same order as that observed in the electrochemical analysis. The simulation suggested that the weaker phosphoric acid adsorption can be attributed to a lowered density of states near the Fermi level due to alloying with transition metals.

Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H+/g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm-1), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m-3) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

One-Step Cationic Grafting of 4-Hydroxy-TEMPO and its Application in a Hybrid Redox Flow Battery with a Crosslinked PBI Membrane.

By using a one-step epoxide ring-opening reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO) and glycidyltrimethylammonium cation (GTMA+ ), we synthesized a cation-grafted TEMPO (g+ -TEMPO) and studied its electrochemical performance against a Zn2+ /Zn anode in a hybrid redox flow battery. To conduct Cl- counter anions, a crosslinked methylated polybenzimidazole (PBI) membrane was prepared and placed between the catholyte and anolyte. Compared to 4-hydroxy-TEMPO, the positively charged g+ - TEMPO exhibits enhanced reaction kinetics. Moreover, flow battery tests with g+ -TEMPO show improved Coulombic, voltage, and energy efficiencies and cycling stability over 140 cycles. Crossover of active species through the membrane was not detected.

Effect of morphology of electrodeposited Ni catalysts on the behavior of bubbles generated during the oxygen evolution reaction in alkaline water electrolysis.

We have investigated the release of active sites blocked by bubbles attached on the surface of catalysts during the oxygen evolution reaction (OER) in alkaline water electrolysis, via the modulation of the wetting properties of the four different morphologies of a nickel catalyst.

Novel O-glycosyl amino acid mimetics as building blocks for O-glycopeptides act as inhibitors of galactosidases.

As potential lead structures for a new class of glycosidase inhibitors the novel O-glycosyl amino acid mimetics 3'-O-[2,6-anhydro-D-glycero-L-gluco-heptitol-1-yl]-L-serine 3 and-L-threonine 4 were synthesized, employing regio- and stereoselective aziridine ring opening methodology. They proved to be stable in the presence of glycosidases and showed competitive inhibition of alpha-galactosidase from Aspergillus niger.