Anion Exchange Membrane Research Articles

Tuning poly(isatin biphenyl) anion exchange membranes by copolymerization and branching

The cardo structure and long side chain of poly(isatin biphenyl) are conducive to the motion and aggregation of cations over mainchain type membranes, therefore it is used as the pristine membrane. It is well known that random copolymerization and branching can effectively modify the configuration and properties of polymers. Herein, we use random copolymerization and branching to improve the behaviors of poly(isatin biphenyl) anion exchange membranes (AEMs). High-curvature random copolymers (QPIDBP-n) and high free volume branched polymers (b-QPIBP-x) are synthesized via polycondensation. The random copolymerization results in the formation of a twisted chain structure, while the introduction of branching agent leads to the formation of orderly stacking of chains. Both of these approaches have been demonstrated to boost the microphase-separated morphology of the pristine polymer. A series of QPIDBP-n and b-QPIBP-x are tested and an optimal ratio is explored. QPIDBP-40 and b-QPIBP-5 exhibit high overall performance. Among the as-prepared membranes, b-QPIBP-5 exhibits the highest conductivity (80 °C, 160.7 mS cm−1) with a swelling ratio of 20.7 %. The residual conductivity of b-QPIBP-5 is 93.1 % after the 1200 h alkali stability test. The cell assembled by b-QPIBP-5 achieves a peak power density of 680 mW cm−2. Moreover, the b-QPIBP-5 based cell holds 88.6 % voltage after the in-situ stability test for 50 h.

Bioadhesive-Inspired Ionomer for Membrane Electrode Assembly Interface Reinforcement in Fuel Cells.

Anion exchange membrane fuel cells promise a sustainable and ecofriendly energy conversion pathway yet suffer from insufficient performance and durability. Drawing inspiration from mussel foot adhesion proteins for the first time, we herein demonstrate catechol-modified ionomers that synergistically reinforce the membrane electrode assembly interface and triple-phase boundary inside catalyst layers. The resulting ionomers present exceptional alkaline stability with only slight ionic conductivity declines after treatment in 2 M NaOH aqueous solution at 80 °C for 2500 h. Adopting catechol-modified ionomer as both anion exchange membrane and binder achieves a single-cell performance increase of 34%, and more importantly, endows fuel cell operation at a current density of 0.4 A cm-2 for over 300 h with negligible performance degradation (with a cell voltage decay rate of 0.03 mV h-1). Combining theoretical and experimental investigations, we reveal the molecular adhesion mechanism between the catechol-modified ionomer and Pt catalyst and illuminate the effect on the catalyst layer microstructure. Of fundamental interest, this bioadhesive-inspired strategy is critical to enabling knowledge-driven ionomer design and is promising for diverse membrane electrode assembly configurational applications.

Low-Cost Self-Reconstructed High Entropy Oxide as an Ultra-Durable OER Electrocatalyst for Anion Exchange Membrane Water Electrolyzer.

Future energy loss can be minimized to a greater extent via developing highly active electrocatalysts for alkaline water electrolyzers. Incorporating an innovative design like high entropy oxides, dealloying, structural reconstruction, in situ activation can potentially reduce the energy barriers between practical and theoretical potentials. Here, a Fd-3m spinel group high entropy oxide is developed via a simple solvothermal and calcination approach. The developed (FeCoMnZnMg)3O4 electrocatalyst shows a near equimolar distribution of all the metal elements resulting in higher entropy (ΔS≈1.61R) and higher surface area. The self-reconstructed spinel high entropy oxide (S-HEO) catalyst exhibited a lower overpotential of 240mV to reach 10mA cm-2 and enhanced reaction kinetics (59mV dec-1). Noticeably, the S-HEO displayed an outstanding durability of 1000h without any potential loss, significantly outperforming most of the reported OER electrocatalysts. Further, S-HEO is evaluated as the anode catalyst for an anion exchange membrane water electrolyzer (AEMWE) in 1m, 0.1m KOH, and DI water at 20 and 60°C. These results demonstrate that S-HEO is a highly attractive, non-noble class of materials for high active oxygen evolution reaction (OER) electrocatalysts allowing fine-tuning beyond the limits of bi- or trimetallic oxides.

Dimensionally stable cellulose acetate-chitosan semi-interpenetrating polymer network as fuel cell anion exchange membrane

Dimensionally stable cellulose acetate-chitosan semi-interpenetrating polymer network as fuel cell anion exchange membrane

Aiming the water transport issues of anion exchange membrane fuel cells by introducing hydrophobic carbon nanotube diffusion layer

The gas diffusion layer (GDL) enhances the transport efficiency of reaction gases and facilitates the removal of accumulated liquid water, thereby improving water management in anion exchange membrane fuel cells (AEMFCs). Carbon nanotubes (CNTs) are recognized as one of the promising materials to optimize mass transport within GDLs. In this study, we successfully synthesized an abundance of CNTs on the surface of commercial gas diffusion media. The as-prepared CNT layer exhibits exceptionally high hydrophobic properties and forms a hierarchically hydrophobic structure combined with the gas diffusion media, effectively enhancing the mass transfer of the membrane electrode assembly (MEA) and reducing ohmic impedance. Under supersaturation conditions, the power density of the MEA containing CNTs reaches 1031.7 mW/cm2, significantly higher than the 760.64 mW/cm2 observed for the commercial GDL. Further testing demonstrates that the MEA containing CNTs exhibits a limiting current density of 2507.4 mA/cm2, which is much superior to the benchmark MEA with the commercial GDL (1591 mA/cm2). Electrochemical impedance spectroscopy analysis reveals that the mass transfer resistance of MEAs with CNTs is lower than that of MEAs with the commercial GDL. More importantly, the phase-field modeling is performed to simulate the transport of the liquid water in the hierarchical GDL.

Graphene oxide nanosheets reinforced quaternized poly(2,6-dimethyl-1,4-phenylene oxide) composite membranes with enhanced hydroxide ions conduction at subzero temperature

The realization of high hydroxide ion conductivity on the premise of enough alkaline stability is basic of the practical application of anion exchange membranes (AEMs). In this research, we propose a facile way to enhance the hydroxide ion conductivity at subzero temperature through constructing multilayered microstructures of AEMs. Graphene oxide (GO) nanosheets and 3,6-diazaspiro[5.5]undecane bromide (DSUBr) are alternately deposited on the surface of a quaternized poly(2,6-dimethyl-1,4-phenylene oxide) (QPPO) membrane with the layer by layer self-assembly process. Multilayered and compact microstructures are retained even if the prepared QPPO/(GO/DSUOH)5 membranes are immersed in 2 M KOH solution for 300 h. The hydroxide ions conduction resistance is reduced, deriving from the well-ordered dispersion of components. For example, the QPPO/2-(GO/DSUOH)5 membrane exhibits the hydroxide ion conductivities of 0.922 mS/cm at −25 °C and 58.5 mS/cm at 80 °C. Furthermore, the prepared AEMs possess the enhanced hydroxide ion conductivity owing to the fine dimension and component stabilities. After the ten-cycle hydroxide ion conductivity stability test, the retention rates of hydroxide ion conductivity are 99.4 % at −25 °C and 105 % at 30 °C. Additionally, the residual hydroxide ion conductivity reaches 61.6 mS/cm at 80 °C in 2 M KOH solution for 624 h. A single fuel cell equipped with the QPPO/2-(GO/DSUOH)5 membrane exhibits the maximum power densities of 80.8 mW/cm2 at 30 °C and 351.6 mW/cm2 at 60 °C.

In Situ-Grown Ultrathin Catalyst Layers for Improving both Proton Exchange Membrane Fuel Cell and Anion Exchange Membrane Fuel Cell Performances.

The mass transport and ion conductivity in the catalyst layer are important for fuel cell performances. Here, we report an in situ-grown ultrathin catalyst layer (UTCL) to reduce the oxygen mass transport and a surface ionomer-coated gas diffusion layer method to reduce the ion conducting resistance. A significantly reduced catalyst layer thickness (ca. 1 μm) is achieved, and coupled with the ionomer introduction method, the ultrathin catalyst layer is in good contact with the membrane, resulting in high ion conductivity and high Pt utilization. This ultrathin catalyst layer is suitable for both proton exchange membrane fuel cells and anion exchange membrane fuel cells, giving peak power densities of 2.24 and 1.11 W cm-2, respectively, which represent an increase of more than 30% compared with the membrane electrode assembly (MEA) fabricated by using traditional Pt/C power catalysts. Electrochemical impedance spectra and limiting current tests demonstrate the reduced charge transfer, mass transfer, and ohmic resistances in the ultrathin catalyst layer membrane electrode assembly, resulting in the promoted fuel cell performances.

Hydrophobic Thiophene Unit Modification for the Construction of Novel Anion Exchange Membranes for High-Speed Transport of Ion Channels

Hydrophobic Thiophene Unit Modification for the Construction of Novel Anion Exchange Membranes for High-Speed Transport of Ion Channels

Operando Raman Spectroscopy Reveals Degradation Byproducts from Ionomer Oxidation in Anion Exchange Membrane Water Electrolyzers.

This work showcases the discovery of degradation mechanisms for nonplatinum group metal catalyst (PGM free) based anion exchange membrane water electrolyzers (AEMWE) that utilize hydroxide ion conductive polymer ionomers and membranes in a zero gap configuration. An entirely unique and customized test cell was designed from the ground up for the purposes of obtaining Raman spectra during potentiostatic operation. These results represent some of the first operando Raman spectroscopy explorations into the breakdown products that are generated from high oxidative potential conditions with carbonate electrolytes. We provide a unique design and fabrication method for three-dimensional (3D) printable flow cells that enable spatially resolved Raman spectra collection from the electrode surface into the bulk electrolyte. It is proposed that the generation of breakdown products from the hydroxide-conductive ionomers and membranes originates from a multistep, free radical reaction pathway resulting in chain scission of the poly aryl backbone. This hypothesis is backed by the detection of carboxylic and aromatic functional group Raman signals from small molecules that had dissolved and diffused into the bulk electrolyte.

Machine Learning-Aided Design of Highly Conductive Anion Exchange Membranes for Fuel Cells and Water Electrolyzers.

Alkaline anion exchange membrane (AEM)-based fuel cells (AEMFCs) and water electrolyzers (AEMWEs) are vital for enabling the efficient and large-scale utilization of hydrogen energy. However, the performance of such energy devices is impeded by the relatively low conductivity of AEMs. The conventional trial-and-error approach to designing membrane structures has proven to be both inefficient and costly. To address this challenge, a fully connected neural network (FCNN) model is developed based on acid-catalyzed AEMs to analyze the relationship between structure and conductivity among 180,000 AEM variations. Under machine learning guidance, anilinium cation-type membranes are designed and synthesized. Molecular dynamics simulations and Mulliken charge population analysis validated that the presence of a large anilinium cation domain is a result of the inductive effect of N+ and benzene rings. The interconnected anilinium cation domains facilitated the formation of a continuous ion transport channel within the AEMs. Additionally, the incorporation of the benzyl electron-withdrawing group heightened the inductive effect, leading to high conductivity AEM variant as screened by the machine learning model. Furthermore, based on the highly active and low-cost monomers given by machine learning, the large-scale synthesis of anilinium-based AEMs confirms the potential for commercial applications.

High-Performance CoCu–N–C/Mo2TiC2–NH4 Catalysts toward the Oxygen Reduction Reaction for Alkaline Anion Exchange Membrane Fuel Cells

High-Performance CoCu–N–C/Mo₂TiC₂–NH₄ Catalysts toward the Oxygen Reduction Reaction for Alkaline Anion Exchange Membrane Fuel Cells

Rationally designed Ru catalysts supported on TiN for highly efficient and stable hydrogen evolution in alkaline conditions

Electrocatalysis holds the key to enhancing the efficiency and cost-effectiveness of water splitting devices, thereby contributing to the advancement of hydrogen as a clean, sustainable energy carrier. This study focuses on the rational design of Ru nanoparticle catalysts supported on TiN (Ru NPs/TiN) for the hydrogen evolution reaction in alkaline conditions. The as designed catalysts exhibit a high mass activity of 20 A mg−1Ru at an overpotential of 63 mV and long-term stability, surpassing the present benchmarks for commercial electrolyzers. Structural analysis highlights the effective modification of the Ru nanoparticle properties by the TiN substrate, while density functional theory calculations indicate strong adhesion of Ru particles to TiN substrates and advantageous modulation of hydrogen adsorption energies via particle-support interactions. Finally, we assemble an anion exchange membrane electrolyzer using the Ru NPs/TiN as the hydrogen evolution reaction catalyst, which operates at 5 A cm−2 for more than 1000 h with negligible degradation, exceeding the performance requirements for commercial electrolyzers. Our findings contribute to the design of efficient catalysts for water splitting by exploiting particle-support interactions.

Inducing Intermolecular Oxygen Coupling by Introducing S and FeOOH on Co(OH)2 Nanoneedle Arrays for Industrial Water Oxidation.

The design of electrocatalysts for oxygen evolution reaction (OER) remains a limitation of industrial hydrogen production by electrolysis of water. Excellent and stable OER catalysts can be developed by activating lattice oxygen and changing the reaction path. Herein, S and FeOOH on the Co(OH)2 nanoneedle arrays are introduced to construct a heterostructure (S-FeOOH/Co(OH)2/NF) as a proof of concept. Theoretical calculations and experimental suggest that the Co-O-Fe motif formed at the heterogeneous interface with the introduction of FeOOH, inducing electron transfer from Co to Fe, enhancing Co─O covalency and reducing intramolecular charge transfer energy, thereby stimulating direct intramolecular lattice oxygen coupling. Doping of S in FeOOH further accelerates electron transfer, improves lattice oxygen activity, and prevents dissolution of FeOOH. Consequently, the overpotential of S-FeOOH/Co(OH)2/NF is only 199mV at 10mA cm-2, and coupled with the Pt/C electrode can be up to 1 A cm-2 under 1.79V and remain stable for over 120h in an anion exchange membrane water electrolyzer (AEMWE). This work proposes a strategy for the design of efficient and stable electrocatalysts for industrial water electrolysis and promotes the commercialization of AEMWE.

Effect of branching degree of quaternized poly(p-terphenyl isatin) on the performance of anion exchange membrane water electrolyzers

Anion exchange membrane (AEM) is a vital component of an anion exchange membrane water electrolyser (AEMWE). Herein, we reported a series of quaternized poly(p-terphenyl isatin) (Q-PPI-bx) AEMs with the branching architecture and microporous structure by incorporating bulky rigid 1,3,5-triphenyl monomer through a superacid polycondensation reaction. It was found that the introduction of branching and microporous structures provided the membranes with a larger free volume and distinct microphase separation morphology, thus resulting in a higher OH− ionic conductivity (158.7 mS cm−1 at 80 °C). At the same time, the AEMs exhibited good mechanical properties and good alkaline stability (retention of 85 % for 1500 h in 1 M KOH at 80 °C). In addition, the current density of Q-PPI-b10 AEM was 1.14 A cm−2 at 2 V in AEMWE. During the in-situ endurance experiment at current density of 0.2 A cm−2, the voltage remained stable for 170 h. These findings underscore the potential of novel branched AEMs for application in AEMWE systems with enhanced performance and durability, thus contributing to the advancement of efficient and sustainable water electrolysis technology.

Highly durable anion exchange membranes with sustainable mitigation of hydroxide attacks for water electrolysis

Low hydroxide conductivity and insufficient alkaline stability are the main problems currently facing anion exchange membranes (AEMs). Conventional quaternary ammonium groups have limited resistance to attack by hydroxide roots. In this paper, quaternary ammonium-type (Cn-PFCO (n = 2, 5)) perfluoroanion exchange polymers with carbonyl side chains were synthesized. The C5–PFCO exhibited an impressive conductivity of 113.4 mS cm−1 at 80 °C, and remarkably, it retained 86.87% of its initial conductivity even after 15 days of immersion in a 1 M KOH aqueous solution. This excellent alkali resistance is due to the generation of intermediate oxygen anions from OH− and carbonyl groups through a reversible reaction. These anions effectively reduce the likelihood of SN2 attack by diminishing the electrostatic potential of the QA groups from Density Functional Theory (DFT) calculations. The electrostatic potential of C2–PFCO is 6.28 eV, while it decreases to 2.69 eV after the formation of intermediate anions. Furthermore, we also used the prepared AEM for pure water electrolysis to explore its performance. The electrochemical performance of AEMWE exhibited remarkable results when supplied with pure water, demonstrating an impressive current density of 262 mA cm−2 at 1.9 V. This study introduces a novel strategy for concurrently enhancing hydroxide conductivity and alkali resistance in AEMs by analyzing the potential for further improvement in AEMs' alkali resistance.

Manipulation of Oxidation States on Phase Boundary via Surface Layer Modification for Enhanced Alkaline Hydrogen Electrocatalysis.

In alkaline water electrolysis and anion exchange membrane water electrolysis technologies, the hydrogen evolution reaction (HER) at the cathode is significantly constrained by a high energy barrier during the water dissociation step. This study employs a phase engineering strategy to construct heterostructures composed of crystalline Ni4W and amorphous WOx aiming to enhance catalytic performance in the HER under alkaline conditions. This work systematically modulates the oxidation states of W within the amorphous WOx of the heterostructure to adjust the electronic states of the phase boundary, the energy barriers associated with the water dissociation step, and the adsorption/desorption properties of intermediates during the alkaline HER process. The optimized catalyst, Ni4W/WOx-2, with a quasi-metallic state of W coordinated by a low oxygen content in amorphous WOx, demonstrates exceptional catalytic performance (22 mV@10mA cm-2), outperforming commercial Pt/C (30 mV@10mA cm-2). Furthermore, the operando X-ray absorption spectroscopy analysis and theoretical calculations reveal that the optimized W atoms in amorphous WOx serve as active sites for water dissociation and the nearby Ni atoms in crystalline Ni4W facilitated the release of H2. These findings provide valuable insights into designing efficient heterostructured materials for energy conversion.

On the selective transport of mixtures of organic and inorganic anions through anion-exchange membranes: A case study about the separation of nitrates and citric acid by electrodialysis

Electrodialysis is finding an increasing number of applications, recently also in the separation and purification of organic acids. This technology involves reducing the use of chemicals and the generation of wastes, as compared to conventionally used processes. Gaining insights about the competitive transport between organic and inorganic ions in ED systems is key to achieving efficient separation processes in the bioresource industry. In the present study, the competitive transport of organic (citrates) and inorganic anions (nitrates) through anion-exchange membranes is investigated, under varying pH conditions, ion concentrations, and applied currents, by means of chronopotentiometry and ED experiments. In the absence of nitrate ions and under acidic conditions (pH 2), the resistance of the membrane system is very high because citric acid is mainly present in its undissociated and uncharged form. In the case of sodium citrate (pH 8), the membrane resistance decreases, especially at high current densities, which promote dissociation reactions and the subsequent concentration increase in ionic species near the membrane. Such phenomenon is identified both in chronopotentiometric curves and in long-term ED experiments by a gradual drop in membrane voltage with time. Although being less concentrated than citrates, the selective removal of nitrates is the most effective choice for the separation of both types of species. The selectivity factor of nitrates over citrates reaches the highest values at low applied current densities (below the limiting current density), with stable permselectivity values higher than 20. Such conditions also lead to the least specific energy consumption per nitrates removed (<0.5 kW·hr·kgNO3--1). Therefore, ED can be used under such favorable operating conditions after a clarification step in order to remove inorganic ions from fermentation broths and increase the purity of organic acids. At higher current densities, the enhanced transport of citrate anions produces a significant drop in selectivity towards nitrates and increases the specific energy consumption.

Electrochemical Performance of a Hybrid NiCo2O4@NiFelt Electrode at Different Operating Temperatures and Electrolyte pH

Transition metals such as nickel and cobalt as an alternative to Pt and Pd can be used for oxygen evolution reactions (OERs) and hydrogen production reactions (HERs) in alkaline environments, facilitating green hydrogen production as a sustainable alternative to fossil fuels. In this study, an NiCo2O4 catalyst was produced by a sono-hydrothermal method using urea as a hydrolysis agent. The electrochemical performance of the catalyst-coated NiFelt electrode was evaluated at different KOH concentrations (0.25, 0.5, and 1 M) and four operating temperatures in the interval of 20–80 °C. The electrode characteristics were investigated via electrochemical spectroscopy (cyclic voltammetry, EIS, multistep chronopotentiometry, multistep chronoamperometry) using two different reference electrodes (Ag/AgCl and Hg/HgO), to obtain insight into the anodic and cathodic peaks. XRD, SEM, EDS, and TEM analyses confirmed the purity, structure, and nanoscale particle size (20–45 nm) of the NiCo2O4 catalyst. The electrode showed symmetric CV with Ag/AgCl, making this reference electrode more appropriate for capacitance measurements, while Hg/HgO proved advantageous for EIS in alkaline solutions due to reduced noise. The overpotential of the catalyst-coated NiFelt decreased by 108 mV at 10 mA/cm2 compared to bare NiFelt, showing a good potential for its application in anion exchange membranes and alkaline electrolyzers at an industrial scale.

Titanium dioxide induced nickel-iron alloy-based precatalyst towards efficient and durable oxygen evolution reaction

Highly active and stable electrocatalysts are essential to facilitate the oxygen evolution reaction (OER) during alkaline water splitting. Herein, a titanium dioxide supported NiFe-based OER electrocatalyst (NiFe/TiO2) was developed through simple impregnation reduction method. The introduction of TiO2 support not only enhances the catalyst stability, but also induces the formation of NiFe alloy pre-catalyst layer on the oxide surface. In situ Raman revealed that the NiFe alloy was partially transformed into highly active NiOOH species in OER process. In situ infrared and theoretical calculations confirm the promoted formation of *OOH intermediate on NiFe/TiO2 surface and thus accelerates the OER. The NiFe/TiO2 catalyst achieves excellent OER activity delivering 10 mA cm−2 at low overpotential of 240 mV in 1.0 M KOH. The anion exchange membrane water electrolyzer with NiFe/TiO2 achieves 500 mA cm−2 with cell voltage of 1.72 V, and good stability is maintained for 300 h. This study advances the effort of developing efficient and durable alkaline OER catalysts.

Single atom catalyst induced by redox reaction between iron ion and aniline monomer

The effective design of a low-cost, efficient, and stable non-noble metal electrocatalyst to substitute the noble metal electrocatalyst for oxygen reduction reaction is highly significant. Even though atomically dispersed metal catalyst shows excellent catalytic activity with maximized atom efficiency, the challenge often lies in achieving uniform distribution for single-atom catalysts owing to their tendency to aggregate. In this work, we present a sequential method that involves the reduction of iron (Fe) mediated by aniline (anchored on support), followed by pyrolysis to fabricate the Fe-Nx moieties and achieve the high density of single atom active sites. The resulting Fe SA 900 catalyst exhibited a half-wave potential of 0.84 V vs. reversible hydrogen electrode (RHE) for oxygen reduction reaction and outstanding stability in alkaline condition. Using various analysis techniques and electrochemical analysis, we demonstrated that the electrocatalytic activity of the catalyst arises from Fe single atom. To validate the practical applicability of Fe-N-C catalysts, we conducted an anion exchange membrane fuel cell (AEMFC) test, which demonstrated a high performance of 212 mW cm−2 at maximum power density. This study proves that the effectiveness of a sequential strategy adopting redox reaction and following pyrolysis for precise synthesis of a single atom Fe catalyst.