A novel anion exchange membrane based on poly (2,6-dimethyl-1,4-phenylene oxide) with excellent alkaline stability for AEMFC

We report a novel comb-shaped anion exchange membrane based on poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and 4-(dimethylamino)butyraldehyde diethyl acetal (DABDA). The Menshutkin reaction successfully introduced DABDA into the brominated PPO backbone, which was proved through FT-IR and ¹H NMR. The distinct hydrophilic/hydrophobic microphase separation structure observed by transmission electron microscope (TEM). As the increase of grafting degree, so does the water uptake, swelling ratio, hydroxide conductivity and alkaline stability. The membranes also possess good mechanical property with tensile strength from 14.2 to 38.11 MPa. This is due to the increasing number of hydroxide and unique steric hindrance effect caused the higher water uptake and higher dimensional stability. Simultaneously, especially PPO/DABDA-60 in comb-shaped membranes demonstrate an excellent long-term alkali resistance stability. In a 576-h alkali resistance stability test, the retained ionic conductivity of the PPO/DABDA-60 membrane is 96% of the initial value. The PPO/DABDA-60 is a potential candidate material for AEM.     

Facile preparation of poly (2,6-dimethyl-1,4-phenylene oxide)-based anion exchange membranes with improved alkaline stability

Traditional quaternary ammonium (QA)-type anion exchange membranes (AEMs) usually exhibit insufficient alkaline stability, which impede their practical application in fuel cells. To address this issue, a facile method for the simple and accessible preparation of QA-type AEMs with improved alkaline stability was developed in this study. A series of novel AEMs (QPPO-xx-OH) were prepared from commercially available poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and 3-(dimethylamino)-2,2-dimethyl-1-propanol, via a three-step procedure that included bromination, quaternization, and ion exchange. Scanning electron microscopy revealed that dense, uniform membranes were formed. These QPPO-xx-OH membranes exhibited moderate hydroxide conductivities with ranges of 4–15 mS/cm at 30 °C and 12–36 mS/cm at 80 °C. When tested at similar ion exchange capacity (IEC) levels, the IEC retentions of QPPO-xx-OH membranes were 16–22% higher than that of traditional PPO membranes containing benzyltriethylammonium ions, after immersed in 2 M NaOH aqueous solution at 60 °C for 480 h, and the QPPO-47-OH membrane displayed excellent alkaline stability with the IEC retention of 92% after 480 h. In addition, the QPPO-xx-OH membranes also exhibited robust mechanical properties (tensile strength up to 37.6 MPa) and good thermal stability (onset decomposition temperature up to 150 °C). This study provides a new and scalable method for the facile preparation of AEMs with improved alkaline stability.     

Anionic membrane and ionomer based on poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline membrane fuel cells

Hydroxyl-ion conductive poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membranes with different characteristics were prepared via relatively simple bromination/amination serial reactions with reduced number of involved chemicals and shorter reaction time. The effects of reactants ratio, reaction atmosphere, polymer concentration, casting solvent, and hydroxylation treatment on reaction were investigated in details. The microstructure, water uptake, swelling ratio, ion-exchange capacity and ionic conductivity of the membranes were also studied. The obtained results demonstrate that, the ionic conductivity of the membrane is dependent on casting solvent. The N-methyl-2-pyrrolidonecast membrane exhibits the highest conductivity with the thinnest film. Although the membrane was prepared via a relatively simple preparation route with least toxic chemicals, a competitive ionic conductivity value of 1.64 × 10⁻² S cm⁻¹ was achieved at 60 °C. A power density of 19.5 mW cm⁻² has been demonstrated from the alkaline membrane fuel cell operated at 70 °C, assembled from the entirely homemade membrane electrode assembly without any hot-pressing.     

Flexibly crosslinked and post-morpholinium-functionalized poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes

Morpholinium-functionalized cross-linked poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) anion exchange membranes were prepared using a crosslinking/post-functionalization method. 4,4'-(oxybis(ethane-2,1-diyl)) dimorpholine (OEDM) having a flexible long chain and hydrophilic ether bond was for the first time used as the crosslinker. The brominated PPO reacted with OEDM, forming a crosslinked structure and accomplishing partial functionalization. Further functionalization was carried out by immersion in N-methylmorpholine aqueous solution. The degree of crosslinking was controlled by varying the proportion of brominated PPO to OEDM because excessive bromomethyl groups ensured the occurrence of crosslinking reaction. The cross-linked structure promoted the formation of micro-phase separation and effectively limited swelling. The crosslinked membrane shows much higher conductivity and lower swelling ratio compared to non-crosslinked one at similar IEC. The highest hydroxide conductivity that the crosslinked membrane achieves is 35 mS cm⁻¹ at 20 °C. The power density for the H₂/O₂ single cell assembled with this membrane is up to 193 mW cm⁻². In addition, the crosslinked PPO-MmOH-Cr membrane exhibits good alkaline stability with conductivity loss of less than 15% after soaking in 1 M KOH for 96 h.     

Highly conductive partially cross-linked poly(2,6-dimethyl-1,4-phenylene oxide) as anion exchange membrane and ionomer for water electrolysis

Cross-linked quaternised Poly(2,6-dimethyl-1,4-Phenylene Oxide) (QPPO)-based membranes were prepared via Friedel-Crafts reactions using SnCl₄ catalyst, 1,3,5-trioxane and chlorotrimethylsilane as environmentally-friendly chloromethylating reagents. New equations to calculate the degree of chloromethylation (DC) and cross-linking degree (CLD) were proposed. Ionic conductivity of 133 mS cm⁻¹ at 80 °C was obtained, one of the highest reported for QPPO based membranes. We have compared QPPO to chloromethylated polystyrene-b-poly(ethylene/butylene)-b-polystyrene (SEBS) ionomer and report on the importance of ionomer-membrane interaction as well as the trade-off between swelling ratio and conductivity on performance and mechanical stability of AEM water electrolyser. Exsitu stability testing after 500 h in 1 M KOH showed membranes retained up to 94% of their original IEC. QPPO was employed as both membranes and ionomers in electrolyser tests. QPPO membranes exhibited area specific resistance of 104 mΩ cm⁻² and electrolyser current density of 814 mA cm⁻² at 2.0 V in 0.1 M NaOH solution at 40 °C.     

Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: Effect of silica content and the single cell performance

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid alkaline membranes with enhanced hydroxyl (OH⁻) conductivity are prepared in response to the relatively low conductivity of previously reported PPO-based systems. The membranes also exhibit higher swelling-resistant properties and the hydroxyl (OH⁻) conductivity values are comparable to previously reported fluoropolymer-containing membranes: 0.012-0.035 S cm⁻¹ in the temperature range 30-90 °C. Other favorable properties for fuel cell application include high tensile strengths up to 25 MPa and large ion-exchange capacities in the range 2.01-2.27 mmol g⁻¹. Beginning-of-life fuel cell testing of a membrane with a thickness of 140 μm yielded an acceptable H₂/O₂ peak power density of 32 mW cm⁻² when incorporated into an alkaline membrane electrode assembly. Therefore, this class of hybrid membrane is suitable for application in alkaline membrane fuel cells.     

A poly (ethylene oxide)/graphene oxide electrolyte membrane for low temperature polymer fuel cells

A novel method to prepare poly (ethylene oxide)/graphene oxide (PEO/GO) composite membrane aimed for the low temperature polymer electrolyte membrane fuel cells without any chemical modification is presented in this work. The membrane thickness is 80 μm with a GO content of 0.5 wt%. And SEM images show the PEO/GO membrane is condensed composite material without structure defects. Small angle XRD results for the membrane samples show that the d-spacing reflection (0 0 1) of GO in PEO matrix is shifted from 2θ = 11° to 4.5° as the PEO molecules intercalated into the GO layers during the membrane preparation process. FTIR tests show the typical -COOH vibration near 1700 cm⁻¹. Tensile tests show the resultant PEO/GO membrane tensile strength of 52.22 MPa and Young's modulus 3.21 GPa, and the fractured elongation was about 5%. The ionic conductivity of this PEO/GO membrane increases from 0.086 to 0.134 S cm⁻¹ when the operation temperature increases from 25 to 60 °C with 100% relative humidity. And further tests show the DC electronic resistance of this membrane is higher than 20 MΩ at room temperature with 100% relative humidity. Polarization curves in a single cell with this membrane give a maximum power density of 53 mW cm⁻² at the operation temperature around 60 °C, without optimizing the catalyst layer composition.     

Well-designed mono- and di-functionalized comb-shaped poly(2,6-dimethylphenylene oxide) based alkaline stable anion exchange membrane for fuel cells

To mitigate the membrane stabilities (dimensional and mechanical) and ionic properties, we report well functionalized hydrophilic and hydrophobic (responsible for stabilities) phase separated quaternized anion exchange membrane (AEM). The N,N,N,N-Tetramethyl-1,3-propanediamine quaternized AEM spliced with alkyl chain (DQCP-36) formed self-amassed morphology with larger ionic clusters. The most suitable optimized AEM (DQCP-36) demonstrated enhanced hydroxide ion conductivity (4.66 × 10^?2 S cm^?1), ion-exchange capacity (1.35 meq./g) and lower activation energy (11.52 kJ/mol). These AEMs showed self-amassed morphology (well balanced hydrophilic and hydrophobic domain) and excellent stabilities (thermal, alkaline and dimensional). Under harsh alkaline medium (2 M NaOH) at 60 °C, DQCP-36 AEM showed about 9% reduction in conductivity after 700 h treatment, and assessment to be a suitable candidate for alkaline fuel cells.     

Preparation and characterization of fluorinated poly(aryl ether oxadiazole)s anion exchange membranes based on imidazolium salts

A series of fluorinated poly(aryl ether oxadiazole)s ionomers based on imidazolium salts (FPAEO-xMIM) were synthesized by quaternization of bromomethylated poly(aryl ether oxadiazole)s (FPAEO-xBrTM) with 1-methyl imidazole as aminating reagent. The anion exchange membranes (AEMs) were prepared by casting method and then immerged in aqueous sodium hydroxide for hydroxide ion exchanging. The structure of the obtained ionomers was characterized by ¹H-NMR and FT-IR measurements. The physical and electrochemical properties of the membranes were also investigated. The hydroxide conductivity of FPAEO-xMIM membranes was higher than 10⁻² S cm⁻¹ at room temperature, while the water uptake and swelling ratio was moderate even at elevated temperature. TGA analysis revealed that the membranes based on imidazolium salts had good thermal stability.     

Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells

Alkaline fuel cells suggest solution for the problems of low methanol oxidation kinetics and methanol crossover, which are limiting the development of direct methanol fuel cells. In this work, a novel anion exchange membrane, quaternized poly(aryl ether oxadiazole), was prepared through polycondensation, grafting and quaternization. The ionic conductivity of as-synthesized anion exchange membrane can reach up to 2.79 × 10⁻² S/cm at 70 °C. The physical and chemical stability of the anion exchange membranes could also meet the requirement for alkaline direct methanol fuel cells.     

Preparation and characterization of nanocomposite membranes made of poly(2,6-dimethyl-1,4-phenylene oxide) and montmorillonite for direct methanol fuel cells

Partially sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (sulfonated PPO) with various degrees of sulfonation were prepared. The solutions were mixed with organically modified montmorillonite (MMT) to prepare membranes by solvent casting. By increasing the sulfonation degree up to 40% for membranes without MMT, ion exchange capacity, water uptake and proton conductivity reached 2.59 mequiv. g⁻¹, 21% and 0.0182 S cm⁻¹, respectively. The Fourier transfer infrared (FTIR) analysis of sulfonated membranes revealed absorption bands at 1060 and 1100–1300 cm⁻¹ for sulfur–oxygen SO bonds. X-ray diffraction analysis showed the exfoliated structure of clay in polymeric matrices. A sulfonated PPO/MMT membrane with 27% sulfonation and 2.0 wt% MMT loading showed a membrane selectivity of approximately 63,500 compared to 40,500 for Nafion^® 117, and also a higher power density (125 mW cm⁻²) than Nafion^® 117 (108 mW cm⁻²) for single cell DMFC in a 5 M methanol feed.     

Synthesis and characterization of quaternary ammonium functionalized fluorene-containing cardo polymers for potential anion exchange membrane water electrolyzer applications

Soluble quaternary ammonium functionalized poly(fluorenyl ether)s (PFEQAs) with a wide range of ion exchange capacities (IECs) were successfully synthesized from a novel tertiary amine group containing cardo monomer. Complete conversion of tertiary amine group to quaternary ammonium group was established, which enables precise control over IEC of the resultant polymers by adjusting monomer-loading ratio. The influence of IEC on the thermal stability, mechanical integrity, water uptake and ion conductivity of the PFEQAs were investigated. Furthermore, four counter ions were selected and their influences on the water uptake and ion conductivity of PFEQAs were studied in detail in order to give a comprehensive view of the transport properties of these anion exchange membranes. It was observed that the water uptakes of the membranes with different counter ions followed the trend: OH⁻ > SO₄²⁻ > Cl⁻ > I⁻ while their ion conductivities followed another trend: OH⁻ > SO₄²⁻ > Cl⁻ > I⁻. These membranes exhibited promising characteristics for anion exchange membrane water electrolyzers working with neutral PH water with or without supporting electrolytes.     

Poly(arylene ether sulfone) with tetra(quaternary ammonium) moiety in the polymer repeating unit for application in solid alkaline exchange membrane fuel cells

Poly(arylene ether sulfone)s with tetra(quaternary ammonium) hydroxide groups in the repeating unit of the polymer main chain were prepared for solid alkaline exchange membrane fuel cells. We synthesized a novel monomer with four amine groups which were derivatized to ammonium functional groups. Using this monomer, we easily synthesized poly(arylene ether sulfone)s which conduct hydroxyl ions. This direct synthetic method can control the exact amount of quaternary ammonium hydroxide groups in the polymer structure. The polymers were characterized by NMR, thermogravimetric analysis, water uptake, conductivity, and cell performance. In a solid alkaline exchange membrane fuel cell test, a maximum power output of 77 mW cm⁻² was achieved using hydrogen and oxygen.     

Direct ethanol fuel cells using an anion exchange membrane

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm⁻² to 58 mW cm⁻² at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.     

Radiation grafted membranes for superior anion exchange polymer membrane fuel cells performance

A study of radiation grafted polymers on the conductivity and performance of alkaline anion exchange membrane fuel cells (AAEMFCs) is reported. The aminated poly (LDPE-g-VBC), poly (HDPE-g-VBC) and poly (ETFE-g-VBC) membranes were produced by the using the radiation grafting technique. Differences in grafting behaviour are observed between the studied materials caused by differences in the base polymer film properties as molar mass, crystallinity, orientation or grafting technique used. In plane conductivities increased with Degree of Grafting DoG. At a DoG of 68% the LDPE-g-VBC membrane achieved an in-plane ionic conductivity between 0.18 and 0.32 S cm⁻¹ in the temperature range 20–80 °C. Measured through plane conductivities were lower than that of the in plane ones for all studied membranes. Membranes with the highest degree of swelling showed the highest through plane conductivity of 0.07–0.11 S cm⁻¹. The membrane specific resistance (per MEA cm²) of most of the produced membranes was in the range of 0.09–0.18 Ω cm². While membrane conductivity and hence IR loss is a crucial factor in fuel cell performance, membrane water permeability is a similarly crucial key for optimised water transport to the cathode. The main source of performance loss of AAEMFCs is believed to be restricted mass transport of water to the cathode reaction sites. The highly humidified anode stream along with large amount of water produced at the anode at high current densities could lead to flooding if water is not removed quickly to the cathode via the membrane (back diffusion) where it is consumed.     

Macromolecular crosslink of imidazole functionalized poly(vinyl alcohol) and brominated poly(phenylene oxide) for anion exchange membrane with enhanced alkaline stability and ionic conductivity

Anion exchange membranes (AEMs) are important energy conversion device for fuel cell applications, where the overall redox reaction happened. Both alkaline stability and ionic conductivity should be considered in the long-term use of fuel cells. In this work, imidazole functionalized polyvinyl alcohol was designed as the functional macromolecular crosslinking agent to fabricate crosslinked AEMs with brominated poly(phenylene oxide) matrix. Benefitting from the macromolecular crosslinked structure, the membranes displayed enhanced ionic conductivity and alkaline stability at elevated temperature. Moreover, membrane with ion exchange capacity of 1.54 mmol/g displayed ionic conductivity of 78.8 mS/cm at 80 °C, and the conductivity could maintain 75% of the initial value after immersion in 1 M NaOH solution at 80 °C for 1000 h. Moreover, a peak power density of 105 mW/cm² was achieved when the assembled single cell with c-91 was operated at 60 °C. These results indicated that the construction of macromolecular crosslinked AEMs have great potential in the practical application of anion exchange membranes fuel cells.     

Quaternized cardo polyetherketone anion exchange membrane for direct methanol alkaline fuel cells

Quaternized cardo polyetherketone (QPEK-C) membranes for alkaline fuel cells were prepared via chloromethylation, quaternization and alkalization of cardo polyetherketone (PEK-C). The chemical reaction for PEK-C modification was confirmed by nuclear magnetic resonance (¹H NMR) and energy-dispersive X-ray spectroscopy (EDAX). The QPEK-C membrane was characterized by X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TG). The ion-exchange content (IEC), water and methanol uptakes, methanol permeability and conductivity of the QPEK-C membranes were measured to evaluate their applicability in alkaline methanol fuel cells. The ionic conductivity of the QPEK-C membrane varied from (1.6 to 5.1) × 10⁻³ S cm⁻² over the temperature range 20-60 °C. The QPEK-C membrane showed excellent methanol resistance. When the concentration of methanol was 4 M, the methanol permeability was less than 10⁻⁹ cm² s⁻¹ at 30 °C.     

Preparation and characterization of imidazolium-functionalized poly (ether sulfone) as anion exchange membrane and ionomer for fuel cell application

Imidazolium-functionalized anion exchange membranes (AEMs) for anion exchange membrane fuel cells (AEMFCs) were synthesized by functionalization of chloromethylated poly (ether sulfone) (PES) with 1-alkylimidazole. The properties of AEMs can be controlled by the degree of chloromethylation of PES. Moreover, with the increment of the alkyl line length on the imidazolium group, the water uptake, swelling ratio and solubility of AEMs increased, whereas the hydroxide conductivity declined. By dissolving AEMs in the mixture of ethanol and water, IM-based anion exchange ionomers (AEIs) can be obtained. Electrochemical studies revealed that the catalytic activities of Pt/C towards oxygen reduction and hydrogen oxidation in the presence of imidazolium-functionalized AEIs were almost the same with that of commercial quaternary ammonium-based ionomers. The fabricated AEM and AEI were utilized to assemble H₂/O₂ AEMFC, yielding a peak power density of ∼30 mW cm⁻² with open circuit potential larger than 1.0 V. The results obtained indicate that imidazolium-functionalized AEMs and AEIs may be candidates which are worth further investigation for the application in the AEMFCs.     

Anion exchange membranes of bis-imidazolium cation crosslinked poly(2,6-dimethyl-1,4- phenylene oxide) with enhanced alkaline stability

Partially crosslinked anion exchange membranes (AEMs) with imidazolium-based cationic functionalities were fabricated based on a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) matrix. The PPO was activated by bromomethylation and functionalized with methylimidazole and 1,4-bis(imidazolyl)butane at different ratios through a gentle and facile heat curing method. The use of 1,4-bis(imidazolyl)butane resulted in a membrane with cationic functionalities incorporated in covalent crosslinks, which allowed for high ion exchange capacities (IECs) without compromising on mechanical robustness. Comprehensive characterizations were performed in terms of thermal stability, water uptake, IEC, swelling, conductivity, mechanical properties and alkaline stability to investigate the correlation of the structure and physicochemical properties. Comparing with the un-crosslinked imidazolium PPO membrane, crosslinked membranes exhibited improved mechanical robustness and alkaline stabilities. The membrane with a crosslinking degree of 10% displayed an IEC of around 1.5 mmol g⁻¹, tensile strength of 4.1 MPa, hydroxide ion conductivity of 40.5 mS cm⁻¹, and a retained ratio in conductivity of 40% after tolerance test of nearly 150 h in 1 mol L⁻¹ KOH (aq.) at 60 °C.     

Anion conductive poly(tetraphenyl phthalazine ether sulfone) containing tetra quaternary ammonium hydroxide for alkaline fuel cell application

The poly(tetraphenyl ether ketone sulfone)s (PTPEKSs) were synthesized from 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenyl benzene (BFBTPB) and bis(4-fluorophenyl) sulfone with bis(4-hydroxydiphenyl) sulfone in sulfolane. The synthesis of poly(tetraphenyl phthalazine ether sulfone)s (PTPPESs) was carried out via an intramolecular ring-closure reaction of dibenzoylbenzene moiety with hydrazine monohydrate. The PTPPES-QAHs [poly(tetraphenyl phthalazine ether sulfone-quaternary ammonium hydroxide)]s were synthesized via chloromethylation of PTPPES, quaternization with trimethylamine, and followed by an anion exchange of tetra-quaternary ammonium chloride polymers with KOH. Different contents of quaternized unit in PTPPES-QAH (15, 20, 25 mol% of BFBTPB) were studied by FT-IR, ¹H NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of quaternized polymers with water. The ion exchange capacity (IEC), ion conductivity and cell performance of PTPPES-QAH were evaluated with increasing the degree of quaternization.