Dense 1,2,4,5-tetramethylimidazolium-functionlized anion exchange membranes based on poly(aryl ether sulfone)s with high alkaline stability for water electrolysis

Anion exchange membranes with enough alkaline stability and ionic conductivity are essential for water electrolysis. In this work, a class of anion exchange membranes (PAES-TMI-x) with dense 1,2,4,5-tetramethylimidazolium side chains based on poly(aryl ether sulfone)s are prepared by aromatic nucleophilic polycondensation, radical substitution and Menshutkin reaction. Their chemical structure and hydrophilic/hydrophobic phase morphology are characterized by hydrogen nuclear magnetic resonance (¹H NMR) and atomic force microscope (AFM), respectively. The water uptake, swelling ratio and ionic conductivity for PAES-TMI-x are in the range of 23.8%–48.3%, 8.3%–14.3% and 18.22–96.31 mS/cm, respectively. These AEMs exhibit high alkaline stability, and the ionic conductivity for PAES-TMI-0.25 remains 86.8% after soaking in 2 M NaOH solution at 80 °C for 480 h. The current density of 1205 mA/cm² is obtained for the water electrolyzer equipped with PAES-TMI-0.25 in 2 M NaOH solution at 2.0 V and 80 °C, and the electrolyzer also has good operation stability at current density of 500 mA/cm². This work is expected to provide a valuable reference for the selection and design of cations in high-performance AEMs for water electrolysis.     

Next-generation anion exchange membrane water electrolyzers operating for commercially relevant lifetimes

Alkaline anion exchange membrane (AEM) water electrolysis has gained increasing attention due to its potential to achieve low-cost, high performance hydrogen production. However, most existing membranes are not durable in industrial settings. Here, we demonstrate good performance relative to industrial parameters using Sustainion® anion exchange membranes. Long-duration tests showed stable performance of 1 A/cm² at 1.85 V with a degradation rate of less than 1 μV/h over 10,000 h. The projected lifetime is thus over 20 years. Daily on/off cycling performance over the course of 30 years was simulated experimentally through accelerated voltage shock tests, resulting in a performance loss of only 0.15 μV/cycle over 11,000 cycles. As shown through impact and crossover testing, an improvement in performance is achieved by the addition of zirconia to the polymer matrix and mechanically reinforcing the membrane.     

Graphene oxide modified non-noble metal electrode for alkaline anion exchange membrane water electrolyzers

This paper reports the performance of a graphene oxide modified non noble metal based electrode in alkaline anion exchange water electrolyzer. The electrolytic cell was fabricated using a polystyrene based anion exchange membrane and a ternary alloy electrode of Ni as cathode and oxidized Ni electrode coated with graphene oxide as anode. The electrochemical activity of the graphene oxide modified electrode was higher than the uncoated electrode. The anion exchange membrane water electrolyzer (AEMWE) with the modified electrode gave 50% higher current density at 30 °C with deionised water compared to that of an uncoated electrode at 2 V. Performance was found to increase with increase in temperature and with the use of alkaline solutions. The results of the solid state water electrolysis cell are promising method of producing low cost hydrogen.     

Accurate evaluation of hydrogen crossover in water electrolysis systems for wetted membranes

In fuel cell and electrolysis systems, hydrogen crossover is a phenomenon where hydrogen molecules (H₂) permeate through a membrane, lowering the overall process efficiency and generating a potential safety risk. Many works have been reported to mitigate this undesired phenomenon, but it is yet difficult to accurately measure the rate of hydrogen crossover, particularly when the membrane is fully wetted in water. In this work, we investigated the pressure decay method as a simple, convenient, and low-cost method to characterize hydrogen crossover through wetted membranes for water electrolysis systems. Three different ion exchange membranes were analyzed: Nafion 212, Nafion 115, and in-house sulfonated poly(arylene ether sulfone). We rigorously confirmed our method and data by comparing it to the ANSI dataset with the current state-of-the-art equations of state (EOS) to account for the nonideality of high pressure hydrogen systems. The error from the gas non-ideality was less than 0.03%. As expected, the rate of hydrogen crossover showed high dependency on the temperature; more importantly, hydrogen crossover increased significantly when the membrane was fully soaked in water. For dry membranes, the proposed pressure decay method corroborated well with the literature data measured using other known methods. Moreover, for wetted membranes, the obtained data showed high similarity compared to the GC method which is currently the most reliable method in the literature. We attempted to predict the hydrogen permeability of wetted membranes using the solution diffusion model. The model based on the given thermodynamic parameters overestimated the hydrogen permeability, which can be used to estimate the ion channel tortuosity.     

Analytical modelling and experimental validation of proton exchange membrane electrolyser for hydrogen production

Proton Exchange Membrane (PEM) Electrolysers (ELSs) are considered as pollution-free with enhanced efficiency technology. Hydrogen can be easily produced from different resources like biomass, water electrolysis, natural gas, propane, and methanol. Hydrogen generation from water electrolysis, which is the splitting of water molecules into hydrogen and oxygen using electricity, can be beneficial when used in combination with variable Renewable Energy (RE) technologies such as solar and wind. When the electricity used for water electrolysis is produced by a variable RE source, the hydrogen stores the unused energy for a later use and can be considered as a renewable fuel and energy resource for the transport and energy sectors.This paper aims to propose a novel graphical model design for the PEM-ELS for hydrogen production based on the electrochemical, thermodynamical and thermal equations. The model under study is experimentally validated using a small-scale laboratory electrolyser. Simulation results, using Matlab-Simulink?, show an adequate parameter agreement with those found experimentally. Therefore, the impact of the different parameters on the electrolyser dynamic performance is introduced and the relevant analytical-experimental comparison is shown. The temperature effect on the PEM-ELS dynamic behaviour is also discussed.     

Development of efficient membrane electrode assembly for low cost hydrogen production by anion exchange membrane electrolysis

Electrochemical production of hydrogen from water using anion exchange membranes (AEMs) can be achieved with non-noble catalysts, other than traditional proton exchange membranes that use platinum group metals. Using non-noble metals in the catalyst layer will reduce the capital costs associated with water electrolysis systems. The objectives of this study were to develop an effective membrane electrode assembly (MEA) for AEM electrolysis and to determine the effects of various operating parameters on AEM electrolysis. Here, the MEA consisted of the commercially available A-201 AEM and non-noble transition metal oxides as catalysts. The best electrolysis performance recorded was 500 mA cm^?2 for 1.95 V at 60 °C with 1% K₂CO₃ electrolyte. For the purpose of comparison, we also considered commercially available AEMs for AEM electrolysis: Fumapem^® FAA-3 and Fumapem^® FAA-3-PP-75. The performances achieved with these AEMs were comparable with the performance recorded for the conventional AEM A-201. Overall, our results indicated that AEM electrolysis clearly manifests the feasibility of commercial viability.     

The importance of OH− transport through anion exchange membrane in microbial electrolysis cells

In two-chamber microbial electrolysis cells (MECs) with anion exchange membranes (AEMs), a phosphate buffer solution (PBS) is typically used to avoid increases in catholyte pH as Nernst equation calculations indicate that high pHs adversely impact electrochemical performance. However, ion transport between the chambers will also impact performance, which is a factor not included in those calculations. To separate the impacts of pH and ion transport on MEC performance, a high molecular weight polymer buffer (PoB), which was retained in the catholyte due to its low AEM transport and cationic charge, was compared to PBS in MECs and abiotic electrochemical half cells (EHCs). In MECs, catholyte pH control was less important than ion transport. MEC tests using the PoB catholyte, which had a higher buffer capacity and thus maintained a lower catholye pH (<8), resulted in a 50% lower hydrogen production rate (HPR) than that obtained using PBS (HPR = 0.7 m³-H₂ m^?3 d^?1) where the catholyte rapidly increased to pH = 12. The main reason for the decreased performance using PoB was a lack of hydroxide ion transfer into the anolyte to balance pH. The anolyte pH in MECs rapidly decreased to 5.8 due to a lack of hydroxide ion transport, which inhibited current generation by the anode, whereas the pH was maintained at 6.8 using PBS. In abiotic tests in ECHs, where the cathode potential was set at ?1.2 V, the HPR was 133% higher using PoB than PBS due to catholyte pH control, as the anolyte pH was not a factor in the performance. These results show that maintaining charge transfer to control anolyte pH is more important than obtaining a more neutral pH catholyte.