Search Results (29)

Developing efficient and durable anion-exchange membranes (AEMs) is essential for advancing electrochemical energy technologies such as water electrolyzers. This study presents a methodological approach for fabricating an AEM by electrospinning a polysulfone (PSU)-based nanofibrous matrix, followed by post-activation using an ionomer solution containing quaternary ammonium (QA) functional groups. Electrospinning is a promising and versatile technique for membrane fabrication, particularly in the context of green hydrogen production via AEM water electrolysis. Its ability to produce nanofibrous matrixes with tunable morphology and properties makes it an attractive alternative to conventional methods for research across various applications. This study demonstrated the feasibility of fabricating electrospun AEMs using polysulfone as a backbone material, suggesting its promise as a potentially scalable solution to manage the high-cost issue of commercial AEMs for future hydrogen production. The resulting composite membrane exhibited ionic conductivity and electrochemical performance comparable to a benchmark membrane fabricated by activating a commercial Celgard 3401 support via phase inversion. Although the mechanical strength of the electrospun membrane was lower than that of the commercial support, its good electrochemical characteristics—combined with the potential for roll-to-roll electrospinning—underscore the promise of this approach as a viable, economically scalable strategy for future hydrogen production WE technologies. Full article

Anion-conducting organic–inorganic polymers (OIPs), constructed using metal–organic framework (MOF)-like structures with non-toxic, non-rare catalytic metals (Fe³⁺, Zr⁴⁺), have been developed. The incorporation of MOF-like structures imparts porosity to the polymers, classifying them as porous organic polymers (POPs). The combination between catalytic activity, ion conduction, and porosity allows the material to act as one-component catalytic electrodes. A high catalytic activity is expected since the entire surface area contributes to electrocatalysis, rather than being restricted to triple-phase boundaries. The synthesis involved anchoring a synthon onto a commercial polymer, assembling organo-metallic moieties, and functionalizing with quaternary ammonium (QA) groups. Two hybrid materials, Zr-POP-QA and Fe-POP-QA, were thoroughly characterized by NMR, FTIR, XPS, BET surface area (≈200 m²/g), and TGA. The resulting electrodes demonstrated a high electrochemically active surface area and a high efficiency for the oxygen reduction reaction (ORR), a critical process for energy storage and conversion technologies. The performance was characterized by a 4-electron reduction pathway, a high onset potential (≈0.9 V vs. RHE), and a low Tafel slope (≈0.06 V). We attribute this efficiency to the high active surface area, which results from the simultaneous presence of catalytic transition metal ions (Zr or Fe) and ion conducting groups. Full article

This study investigates the development of pore-filling anion-exchange membranes (PFAEMs) for water-electrolysis applications. Ionomers using two different cross-linking monomers, namely hydrophilic C10 and hydrophobic C11, along with a common electrolyte monomer, E3, were compared in terms of through-plane ion conductivity, hydrogen permeability, mechanical and chemical stability, I-V polarization, and water-electrolysis durability. The results revealed that the E3-C10 PFAEM exhibited 40% higher OH⁻ conductivity (98.7 ± 7.0 mS cm⁻¹) than the E3-C11 PFAEM with a similar ion-exchange capacity. This improvement was attributed to improved separation of hydrophobic and hydrophilic domains, creating well-connected ion channels by the hydrophilic C10. Alkaline stability tests demonstrated that the E3-C10 retained higher ion conductivity compared to E3-C11, due to the absence of ether linkages and increased resistance to nucleophilic attack. During water-electrolysis operations, the E3-C10 PFAEMs showed 10% better durability and 87% lower hydrogen permeability, confirming their suitability for anion-exchange-membrane water electrolysis (AEMWE). Despite the higher ion conductivity of the E3-C10 PFAEM, performance was limited by interfacial resistance. It is suggested that ionomer-coated electrodes could further enhance AEMWE performance by leveraging the higher ion conductivity of the E3-C10. Overall, this study provides valuable guidance on strategies for utilizing pore-filling membranes in water electrolysis. Full article

This study investigated the modification of nanosilver (Ag) by Co-Pc (phthal–cyanine) and the synergistic effect of Ag-Co/CNT (carbon nanotube) for the long-term stability of AEMFCs (anion exchange membrane fuel cells). This study also aimed to use non-precious metal catalysts on both the cathode and anode to reduce the catalyst costs. Through a simple and efficient chemical synthesis method, a composite catalyst consisting of Co-Pc-modified Ag/CNT was successfully prepared and characterized for its structure and composition. Co-Pc and Ag were chosen for their high durability and catalytic activity in fuel cells, combined with a multi-wall carbon nanotube (MWCNT) as a carrier for the cathode catalyst, and the anode catalyst used Pd-CeO₂/C. The performance of the cell module was tested based on a commercial anion exchange membrane (X37-50RT). The experiment focused on different synthesis times and ratios of catalyst and ionomer, observing the enhancement in Co on the active sites of Ag/CNT. Finally, the cell performance was tested for the optimal loading amount. It was observed that when the loading of the nanosilver–cobalt/carbon nanotube (Ag-Co/CNT) is 1 mg/cm², the highest power density is 434.1 mW/cm². Through 100 cycles of testing, only an 18% decrease was observed, while the decrease in open circuit voltage was approximately 4.6%. Compared to nanosilver (Ag/CNT), the Co-Pc-modified nano-Ag with the degradation rate has significantly slowed down, and its catalytic activity has also improved significantly. The enhanced stability of this synergistic effect is mainly attributed to the introduction of cobalt metal, which prevents excessive fusion of nano-Ag particles and surface oxidation, effectively maintaining durability in catalytic activity. Full article

Anion Exchange Membranes (AEMs) are promising materials for electrochemical devices, such as fuel cells and electrolyzers. However, the main drawback of AEMs is their low durability in alkaline operating conditions. A possible solution is the use of composite ionomers containing inorganic fillers stable in a basic environment. In this work, composite anion exchange membranes are prepared from poly (2,6-dimethyl-1,4-phenylene oxide) with quaternary ammonium groups on long-side chains (PPO-LC) and exfoliated Mg/Al lamellar double hydroxide (LDH) as inorganic filler added in different percentages (2, 5, and 10%). The mechanical stiffness of the membranes increases significantly by the addition of exfoliated LDH up to 5%. The ionic conductivity is measured as a function of the temperature in fully humidified conditions and as a function of relative humidity (RH). The maximum conductivity is observed for 5% LDH. The average activation energy for conductivity amounts to 0.20 ± 0.01 eV in fully humidified conditions and >50% RH. Thermogravimetric analysis of membranes before and after alkaline degradation tests (2 M KOH @ 80 °C, 48 h) reveals that the sample with 5% LDH has improved stability (19% vs. 36% of degradation). The stability tests are also investigated, measuring the ionic conductivity and the water uptake. A protective effect of LDH on the alkaline degradation of quaternary ammonium groups is clearly evidenced and opens the way to the use of different compounds and exfoliation methods in the LDH family. Full article

This work aims at the effects of anion-exchange membranes (AEMs) and ionomer binders on the catalyst electrodes for anion-exchange membrane fuel cells (AEMFCs). In the experiments, four metal catalysts (nano-grade Pt, PtRu, PdNi and Ag), four AEMs (aQAPS-S8, AT-1, X37-50T and X37-50RT) and two alkaline ionomers (aQAPS-S14 and XB-7) were used. They were verified through several technical parameters examination and cell performance comparison for the optimal selection of AMEs. The bimetallic PdNi nanoparticles (PdNi/C) loaded with Vulcan XC-72R carbon black were used as anode electrodes by using the wet impregnation method, and Ag nanoparticles (Ag/C) were used as the catalyst cathode. It was found that the power density and current density of the X37-50RT are higher than the other three membranes. Also, alkaline ionomers of XB-7 had better performance than aQAPS-S14. The efficiency was improved by 32%, 155% and 27%, respectively, when compared to other membranes by using the same catalyst of PdNi/C, Ag/C and Pt/C. The results are consistent with the membrane ion conductivity measurements, which showed that the conductivity of the X37-50RT membrane is the highest among them. The conductivity values for hydroxide ions (OH⁻) and bromide ions (Br⁻) are 131 mS/cm and 91 mS/cm, respectively. These findings suggest that the properties (water uptake, swelling rate and mechanical) of the anion-exchange membrane (AEM) can serve as a key reference for AEM fuel cell applications. Full article

Hydrothermal carbonization (HTC) serves as a sustainable method to transform pine needle waste into nitrogen-doped (N-doped) hydrochars. The primary focus is on evaluating these hydrochars as catalytic electrodes for the oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO₂RR), which are pivotal processes with significant environmental implications. Hydrochars were synthesized by varying the parameters such as nitrogen loading, temperature, and residence time. These materials were then thoroughly characterized using diverse analytical techniques, including elemental analysis, density measurements, BET surface area analysis, and spectroscopies like Raman, FTIR, and XPS, along with optical and scanning electron microscopies. The subsequent electrochemical assessment involved preparing electrocatalytic inks by combining hydrochars with an anion exchange ionomer (AEI) to leverage their synergistic effects. To the best of our knowledge, there are no previous reports on catalytic electrodes that simultaneously incorporate both a hydrochar and AEI. Evaluation metrics such as current densities, onset and half-wave potentials, and Koutecky–Levich and Tafel plots provided insights into their electrocatalytic performances. Notably, hydrochars synthesized at 230 °C exhibited an onset potential of 0.92 V vs. RHE, marking the highest reported value for a hydrochar. They also facilitated the exchange of four electrons at 0.26 V vs. RHE in the ORR. Additionally, the CO₂RR yielded valuable C₂ products like acetaldehyde and acetate. These findings highlight the remarkable electrocatalytic activity of the optimized hydrochars, which could be attributed, at least in part, to their optimal porosity. Full article

Perfluorosulfonated anionic ionomers are known for their robust ion conductivity and chemical and mechanical stability. However, the structure and transport property degradation of perfluorinated cationic polymers (PfCPs) are not well understood. Herein, we propose an ion-exchange strategy to identify the structural degradation, ion transport mechanisms, and architectural reformation of PfCPs. Particularly, we demonstrate that the utility of a –SO₂–N⁺ strategy employing the Menshutkin reaction cannot yield reliable PfCPs and anion-exchange membranes, but can yield an unreliable zwitterionic intermediate (cations–anions molar ratio is approximately 7.6%). Moreover, the degradation products were efficiently reformed as proton exchange membranes (PEMs), and the as-reformed PEMs achieved an ion-exchange capacity (IEC) value (0.89 mmol g⁻¹), meanwhile retaining more than 94.7% of their initial capacity. Furthermore, the fuel cell assembled with reformed PEMs displayed a power density of 0.91 Wcm⁻² at 2.32 A cm⁻², which was 90.1% of that of the robust perfluorosulfonic acid PEMs. Our combined findings shed some fresh light on the state of understanding of the structure–property relationship in PfCPs. Full article

In this study, the optimal fabrication parameters of a heterogeneous anion-exchange membrane (AEM) using an ionomer binder are investigated to improve the performance of continuous electrodeionization (CEDI) for producing ultrapure water. Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is selected as the base material for preparing the ionomer binder and quaternized to have various ion exchange capacities (IECs). The optimal content of ion-exchange resin (IER) powder according to the IEC of the ionomer binder is then determined through systematic analyses. In conclusion, it is revealed that a heterogeneous AEM with optimal performance can be fabricated when the IEC of the ionomer binder is lowered and the content of IER powder is also lower than that of conventional heterogeneous membranes. Moreover, crosslinked quaternized PPO (QPPO) nanofiber powder is used as an additive to improve ion conductivity without deteriorating the mechanical properties of the membrane. The membrane fabricated under optimal conditions exhibits significantly lower electrical resistance (4.6 Ω cm²) despite a low IER content (30 wt%) compared to the commercial membrane (IONAC MA-3475, 13.6 Ω cm²) while also demonstrating moderate tensile strength (9.7 MPa) and a high transport number (ca. 0.97). Furthermore, it is proven that the prepared membrane exhibits a superior ion removal rate (99.86%) and lower energy consumption (0.35 kWh) compared to the commercial membrane (99.76% and 0.4 kWh, respectively) in CEDI experiments. Full article

Studies have been carried out to optimize the composition, formation technique and test conditions of membrane electrode assemblies (MEA) of hydrogen–oxygen anion-exchange membranes fuel cells (AEMFC), based on Fumatech anion-exchange membranes. A non-platinum catalytic system based on nitrogen-doped CNT (CNT_N) was used in the cathode. PtMo/CNT_N catalysts with a reduced content of platinum (10–12 wt.% Pt) were compared with 10 and 60 wt.% Pt/CNT_N at the anode. According to the results of studies under model conditions, it was found that the PtMo/CNT_N catalyst is significantly superior to the 10 and 60 wt.% Pt/CNT_N catalyst in terms of activity in the hydrogen oxidation reaction based on the mass of platinum. The addition of the Fumion ionomer results in minor changes in the electrochemically active surface area and activity in the hydrogen oxidation reaction for each of the catalysts. In this case, the introduction of ionomer–Fumion leads to a partial blocking of the outer surface and the micropore surface, which is most pronounced in the case of the 60Pt/CNT_N catalyst. This effect can cause a decrease in the characteristics of MEA AEMFC upon passing from 10PtMo/CNT_N to 60Pt/CNT_N in the anode active layer. The maximum power density of the optimized MEA based on 10PtMo/CNT_N was 62 mW cm⁻², which exceeds the literature data obtained under similar test conditions for MEA based on platinum cathode and anode catalysts and Fumatech membranes (41 mW cm⁻²). A new result of this work is the study of the effect of the ionomer (Fumion) on the characteristics of catalysts. It is shown that the synthesized 10PtMo/CNT_N catalyst retains high activity in the presence of an ionomer under model conditions and in the MEA based on it. Full article

Low-cost anion exchange membrane (AEM) water electrolysis is a promising technology for producing “green” high-purity hydrogen using platinum group metal (PGM)-free catalysts. The performance of AEM electrolysis depends on the overall overvoltage, e.g., voltage losses coming from different processes in the water electrolyzer including hydrogen and oxygen evolution, non-faradaic charge transfer resistance, mass transfer limitations, and others. Due to the different relaxation times of these processes, it is possible to unravel them in the frequency domain by electrochemical impedance spectroscopy. This study relates to solving and quantifying contributions to the total polarization resistance of the AEM water electrolyzer, including ohmic and charge transfer resistances in the kinetically controlled mode. The high-frequency contribution is proposed to have non-faradaic nature, and its conceivable nature and mechanism are discussed. The characteristic frequencies of unraveled contributions are provided to be used as benchmark data for commercially available membranes and electrodes. Full article

In this work, the preparation of dense blended membranes, from blends of poly(vinylidene fluoride) (PVDF), poly(ether sulfone) (PES) and polyethyleneimine (PEI) or Fumion^®, with possible applications in alkaline fuel cell (AEMFC) is reported. The blended PEI/Fumion^® membranes were prepared under a controlled air atmosphere by a solvent evaporation method, and were characterized regarding water uptake, swelling ratio, thermogravimetric analysis (TGA), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), ion exchange capacity (IEC), OH⁻ conductivity and novel hydroxide ion exchange rate (HIER), which is related to the mass transport capacity of the OH⁻ ions through the membrane. The effect of the chemical composition on its morphological and anion exchange properties was evaluated. It was expected that the usage of a commercial ionomer Fumion^®, in the blended membranes would result in better features in the electrical/ionic conductivity behaviour. However, two of the membranes containing PEI exhibited a higher HIER and OH⁻ conductivity than Fumion^® membranes, and were excellent option for potential applications in AEMFC, considering their performance and the cost of Fumion^®-based membranes. Full article

This work studied the polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) triblock copolymers functionalized by butyl quaternary ammonium (C₄Q) groups and alkyl side chains of different chain lengths (C_n, n = 0 to 24). The hydrated membrane morphology was modeled by dissipative particle dynamics simulation at hydration levels from 10 to 30. A hydroxide model was devised to characterize the diffusivity of anions under the coarse-grained framework. In general, the ionomers with alkyl side chains provided ion conductivity of a similar level at a lower ion exchange capacity. All hydrated SEBS–C₄Q–C_n ionomers showed clear phase separation of the hydrophobic and hydrophilic domains, featuring 18.6 mS/cm to 36.8 mS/cm ion conductivity. The hydrophilic channels expanded as the water content increased, forming more effective ion conductive pathways. Introducing excess alkyl side chains enhanced the nano-segregation, leading to more ordered structures and longer correlation lengths of the aqueous phase. The membrane morphology was controlled by the length of alkyl side-chains as well as their tethering positions. Ionomers with functionalized side chains tethered on the same block resulted in well-connective water networks and higher conductivities. The detailed structural analysis provides synthesis guidelines to fabricate anion exchange membranes with improved performances. Full article

This short review summarizes the improvements on biological fuel cells (BioFCs) with or without ionomer separation membrane. After a general introduction about the main challenges of modern energy management, BioFCs are presented including microbial fuel cells (MFCs) and enzymatic fuel cells (EFCs). The benefits of BioFCs include the capability to derive energy from waste-water and organic matter, the possibility to use bacteria or enzymes to replace expensive catalysts such as platinum, the high selectivity of the electrode reactions that allow working with less complicated systems, without the need for high purification, and the lower environmental impact. In comparison with classical FCs and given their lower electrochemical performances, BioFCs have, up to now, only found niche applications with low power needs, but they could become a green solution in the perspective of sustainable development and the circular economy. Ion exchange membranes for utilization in BioFCs are discussed in the final section of the review: they include perfluorinated proton exchange membranes but also aromatic polymers grafted with proton or anion exchange groups. Full article

In this paper, we simulate the changes in the structure and transport properties of an anion-exchange membrane (CJMA-7, Hefei Chemjoy Polymer Materials Co. Ltd., China) caused by its modification with a perfluorosulfonated ionomer (PFSI). The modification was made in several stages and included keeping the membrane at a low temperature, applying a PFSI solution on its surface, and, subsequently, drying it at an elevated temperature. We applied the known microheterogeneous model with some new amendments to simulate each stage of the membrane modification. It has been shown that the PFSI film formed on the membrane-substrate does not affect significantly its properties due to the small thickness of the film (≈4 µm) and similar properties of the film and substrate. The main effect is caused by the fact that PFSI material “clogs” the macropores of the CJMA-7 membrane, thereby, blocking the transport of coions through the membrane. In this case, the membrane microporous gel phase, which exhibits a high selectivity to counterions, remains the primary pathway for both counterions and coions. Due to the above modification of the CJMA-7 membrane, the coion (Na⁺) transport number in the membrane equilibrated with 1 M NaCl solution decreased from 0.11 to 0.03. Thus, the modified membrane became comparable in its transport characteristics with more expensive IEMs available on the market. Full article