Simultaneously enhanced hydroxide conductivity and mechanical properties of quaternized chitosan/functionalized carbon nanotubes composite anion exchange membranes

Low-cost biopolymer chitosan has received considerable attention in the field of anion exchange membranes (AEMs) because it can be easily quaternized and avoids the carcinogenic chloromethylation step. Simultaneously increasing the ionic conductivity and improving mechanical properties of quaternized chitosan (QCS) is key for its high-performance application. In this study, new composite AEMs consisting of QCS and functionalized carbon nanotubes (CNTs) were prepared. CNTs were coated with a thick silica layer onto which high-density quaternary ammonium groups were then grafted. The insulator silica coating effectively prohibits electron conduction among nanotubes and the grafted –NR₃⁺ provides new OH⁻ conductive sites. Incorporating 5 wt% functionalized CNTs into the matrix enhanced ionic conductivity to 42.7 mS cm⁻¹ (80 °C) which was approximately 2 times higher than that of pure QCS. The effective dispersion of CNTs and appropriate interfacial bonding between nanofiller and QCS improved the mechanical properties of AEMs, including both the strength and toughness of the composite membranes. An alkaline direct methanol fuel cell equipped with the composite membrane (5% functionalized CNTs loading) produced an maximum power density of 80.8 mW cm⁻² (60 °C), which was 57% higher than that of pure QCS (51.5 mW cm⁻²). This study broadens the application of natural polymers and provides a new way to design and fabricate composite AEMs with both improved mechanical properties and electrochemical performance.     

Synthesis and characterization of crosslinked poly (vinyl alcohol)/layered double hydroxide composite polymer membranes for alkaline direct ethanol fuel cells

The low ionic conductivity and low thermal stability of conventional quaternary ammonium group functionalized anion-exchange membranes (AEM) are two key parameters that limit the performance of AEM direct ethanol fuel cells (AEM DEFCs). The present work is to address these issues by synthesizing crosslinked poly (vinyl alcohol)/layered double hydroxide (PVA/LDH) hybrid membranes with solution casting method. The experimental results indicate that incorporating 20 wt.% LDH into the PVA resulted in not only a higher ionic conductivity, but also a lower ethanol permeability. The performance test of the DEFC using the PVA/LDH hybrid membrane shows that the fuel cell can yield a power density of 82 mW cm⁻² at 80 °C, which is much higher than that of the AEM DEFC employing the quaternary ammonium group functionalized membrane. A constant current discharge test shows that the PVA/20LDH membrane can be operated stably at relatively high temperatures.     

Anion exchange membranes composed of quaternized polybenzimidazole and quaternized graphene oxide for glucose fuel cell

Glucose is one of derivative products from agriculture, possessing high theoretical energy density, non-toxicity and ease of storage, which has been of interest as a fuel in glucose fuel cell. In this work, quaternized polybenzimidazole (Q-PBI) and quaternized graphene oxide (Q-GO) were successfully functionalized by the quaternization between polybenzimidazole (PBI) and 3-bromopropyl trimethylammonium bromide (3-Br), and the reaction between graphene oxide (GO) and dimethyloctadecyl [3(Trimethoxysilyl) propyl]ammonium chloride (DMAOP), respectively. The Q-GOs with various volume fractions were embedded as the dispersed phase in the Q-PBI matrix to produce the Q-GO/Q-PBI composites as an AEM. The 0.5%v/vQ-GO/Q-PBI composite AEM showed the highest hydroxide conductivity of 1.12 ± 0.01 mS cm^?1 at 27 °C, the ion exchange capacity of 1.70 ± 0.03 mmol·g^?1, the water uptake of 66.61 ± 0.57%, and the glucose permeability of (1.79 ± 0.83) × 10^?8 cm²·s^?1. The hydroxide conductivity was higher than the commercial Fumasep® FAB-PK-130 by a factor of 23 times, whereas the glucose permeability was lower by at least an order of magnitude.     

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.     

Crosslinked anion exchange membranes with regional intensive ion clusters prepared from quaternized branched polyethyleneimine/quaternized polysulfone

A series of anion exchange membranes (AEMs) with regionally dense ion clusters are prepared by crosslinking quaternized polysulfone (QPSU) with quaternized branched polyethyleneimine (QBPEI). For the as-prepared QPSU/QBPEI AEMs, the hydrophilic QBPEI forms locally aggregated ion clusters in the QPSU matrix, which can promote the formation of an obvious microphase separation structure in the membrane. The QPSU/QBPEI-3 AEM with an ion exchange capacity of 1.88 meq/g exhibits the best performance, achieving a reasonably high ionic conductivity of 66.14 mS/cm at 80 °C and showing good oxidation stability and alkali resistance. Finally, the maximum power density of a single H₂/O₂ fuel cell with QPSU/QBPEI-3 AEM reaches 75.34 mW/cm² at 80 °C. The above results indicate that QBPEI with a dendritic structure and abundant anionic conductive groups has a good application prospect in the preparation of AEMs with locally aggregated ion clusters and microphase separation structures.     

Preparation and characterization of imidazolium-based membranes for anion exchange membrane fuel cell applications

New anion exchange membranes (AEMs) with high conductivity, good dimensional and alkaline stability are currently required in order to develop alkaline fuel cells into efficient and clean energy conversion devices. In this study, a series of AEMs based on 1, 2-dimethyl-3-(4-vinylbenzyl) imidazolium chloride ([DMVIm][Cl]) are prepared and investigated. [DMVIm][Cl] is synthesized and used as ion carriers and hydrophilic phase in the membranes. The water uptake, swelling ratio, IEC and conductivity of the AEMs increase with increasing the [DMVIm][Cl]. The imidazolium-based AEMs show excellent thermal stability, sufficient mechanical strength, the membrane which containing 30% mass fraction of [DMVIm][Cl] shows conductivity up to 1.0 × 10^?2 S cm^?1 at room temperature and good long-term alkaline stability in 1 M KOH solution at 80 °C. The results of this study suggest that this type of AEMs have good perspectives for alkaline anion exchange membrane fuel cell applications.     

Synthesis and characterization of PEEK containing imidazole for anion exchange membrane fuel cell

We synthesized a poly(ether-ether-ketone), containing bisphenol A and tetra imidazolium in the polymer chain using the direct conversion method and condensation reaction. First, we synthesized a tetra-ammonium monomer, which was then converted to ammonium to imidazolium functional groups. Then we tested the alkaline-exchange properties of a prepared polymeric membrane with different contents of the imidazolium moiety for fuel-cell applications. The prepared membranes were characterized in terms of ion exchange capacity, water uptake, mechanical properties, and ion conductivity. The ion exchange capacity and hydroxide conductivity of the prepared membranes were found to increase with increasing amount of functional groups on the membrane.     

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.     

Quaternized poly(vinyl alcohol)/alumina composite polymer membranes for alkaline direct methanol fuel cells

The quaternized poly(vinyl alcohol)/alumina (designated as QPVA/Al₂O₃) nanocomposite polymer membrane was prepared by a solution casting method. The characteristic properties of the QPVA/Al₂O₃ nanocomposite polymer membranes were investigated using thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cell (ADMFC) comprised of the QPVA/Al₂O₃ nanocomposite polymer membrane were assembled and examined. Experimental results indicate that the DMFC employing a cheap non-perfluorinated (QPVA/Al₂O₃) nanocomposite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC with 4 M KOH + 1 M CH₃OH, 2 M CH₃OH, and 4 M CH₃OH solutions are 28.33, 32.40, and 36.15 mW cm⁻², respectively, at room temperature and in ambient air. The QPVA/Al₂O₃ nanocomposite polymer membranes constitute a viable candidate for applications on alkaline DMFC.     

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.     

N-spirocyclic ammonium-functionalized graphene oxide-based anion exchange membrane for fuel cells

Graphene oxide (GO) is a potential material in the electrode and membrane of polymer electrolyte membrane fuel cells due to its unique structure and various oxygen-containing functional groups. A class of three-layered GO/poly (phenylene oxide) for AEMs was prepared in this work. GO was functionalized with highly stable 6-azonia-spiro [5.5]undecane groups and used as a fast hydroxide conductor, named ASU-GO. Functionalized by N-spirocyclic cations, poly (phenylene oxide) (PIPPO) was then combined with ASU-GO and GO to fabricate the ASU-GO/PIPPO and GO/PIPPO. Notably, the maximum hydroxide conductivity of the ASU-GO/PIPPO was 73.7 mS cm⁻¹ at 80 °C, which was 3 times higher than that of the GO/PIPPO. The enhancement in hydroxide conductivity was due to the changes in the hydroxide transport mechanism and the poor stacked structure of the ASU-GO layer. Only 10.8% drops in hydroxide conductivity of ASU-GP/PIPPO after the alkaline test (1 M KOH at 80 °C for 700 h). Furthermore, the ASU-GO/PIPPO-50 membrane showed a maximum peak power density of 102 mW cm⁻², demonstrating the prepared membrane was promising in the AEM applications.     

In-situ preparation of cross-linked hybrid anion exchange membrane of quaternized poly (styrene-b-isobutylene-b-styrene) covalently bonded with graphene

Introducing graphene into polymer matrix is an effective way to enhance performances of anion exchange membrane (AEM). However, utilizing the advantages of graphene by physical approach is limited due to the weak interface interaction between graphene and polymer matrix. Herein, we report an effective strategy to covalently bond graphene with polymer matrix to improve the interface interaction and further to improve the properties of AEM. A series of cross-linked quaternized graphene-based hybrid AEM were fabricated by covalently bonding poly (vinylbenzyl chloride) grafted graphene (GN-g-PVBC) copolymer with chloromethyl functionalized poly (styrene-b-isobutylene-b-styrene) (SIBS) through the cross-linker (N,N,N′,N′-tetramethyl-1,6-hexanediamine) by in-situ synthetic approach. The interface interaction between graphene and QSIBS is greatly enhanced according to micromorphology characterization of the hybrid membrane. The cross-linked quaternized hybrid AEM containing 0.55 wt% of GN-g-PVBC exhibits obviously improved dynamical mechanical properties (storage modulus: 418 MPa), ion conductivity (1.81 × 10² S cm^?1), methanol barrier property (5.19 × 10^?7 cm² s^?1), selectivity (3.49 × 10⁴ S s cm^?3) at 60 °C and especially a comparably excellent chemical stability to that of Nafion 115 due to the enhanced interface interaction between graphene and the polymer matrix.     

Guanidinium cationic covalent organic nanosheets-based anion exchange composite membrane for fuel cells

Covalent organic frameworks (COFs) used for anion exchange membrane fuel cells (AEMFCs) are commonly endowed with ion conductivity by post-synthesis modification. However, this method usually results in uneven distribution of functional groups, low functionalization and severe ion capacity fade. Limited by hydrophobic skeleton and relatively large particle size of COFs, the COFs doping amount of the composite membrane is not high. Here we design and synthesize a series of guanidinium cationic covalent organic nanosheets-based anion exchange composite membranes. The positively charged guanidinium group as a building block can induce COF-DhaTG_Cl self-exfoliation into a few layered nanosheets through strong interlayer repulsion. Then, the nanosheets were introduced into quaternary ammonium-functionalized poly(2,6-dimethyl-1,4-phenyl ether) (QPPO). A series of COF-DhaTG_Cl/PPO composite AEMs was prepared with the highest doping amount of 30 wt% by casting method. The porous structure and repeat cationic guanidinium units on the skeleton will expose ion sites to the target ones, providing faster OH⁻ diffusion kinetics in one-dimensional channels. The OH⁻ conductivity of COF-DhaTG_Cl/PPO-20 composite membrane can reach 148.65 mS/cm at 80 °C. Meanwhile, the composite membrane also exhibits enhanced mechanical strength and alkaline stability with the maximum stress strength of 37.3 MPa and the residual conductivity of 96.29% after immersion in 2 M NaOH solution at 60 °C for two weeks.     

Facile construction of poly(arylene ether)s-based anion exchange membranes bearing pendent N-spirocyclic quaternary ammonium for fuel cells

Anion exchange membrane (AEM) fuel cells have received significant attention due to their low fuel permeability and the use of non-platinum catalysts. However, the development of AEMs with robust chemical stability and high conductivity is still a great challenge. Herein, we prepare a new type of partially fluorinated backbone bearing pendent N-spirocyclic quaternary ammonium (QA) cations via a facile Williamson reaction, which displays great potential for fuel cells. The integration of the two substructures (a fluorinated moiety into a polymer backbone and a pendent cation structure) is beneficial for the fabrication of a well-defined micro-phase separation structure, thereby facilitating the construction of a highly-efficient ion transporting pathway. Correspondingly, the resulting AEM (PAENQA-1.0), despite its a relatively low ionic exchange capacity (0.93 meq g⁻¹) demonstrates a conductivity of 63.1 mS cm⁻¹ (80 °C). Meanwhile, the constrained ring conformation of N-spirocyclic QA results in improved stability of the AEMs.     

Application of 2D nanomaterial MXene in anion exchange membranes for alkaline fuel cells: Improving ionic conductivity and power density

Two types of new 2D MXenes (LiF–Ti₃C₂T_x and NH₄HF₂–Ti₃C₂T_x) were prepared by selective etching of Ti₃AlC₂ with LiF/HCl and NH₄HF₂ aqueous solutions, respectively, and they were introduced as nanofillers into quaternized polysulfone/polyquaternium-10 (QPSU/PQ-10) anion exchange membranes (AEMs) with semi-interpenetrating polymer network, thereby preparing two types of MXene-doped QPSU/PQ-10 AEMs. The resulting MXene-doped QPSU/PQ-10 AEMs have obvious nanoscale microphase-separated morphologies, and their ionic conductivity and power density are significantly improved compared with the pristine QPSU/PQ-10 AEM. Among them, the ionic conductivity and power density of NH₄HF₂–Ti₃C₂T_x MXene-doped AEM can reach 88.76 mS/cm at 80 °C and 106.28 mW/cm² at 60 °C, respectively, which are 26.3% and 37.5% higher than those of the pristine QPSU/PQ-10 AEM. Additionally, the MXene-doped QPSU/PQ-10 AEMs with semi-interpenetrating network have moderate water uptake and swelling ratio, excellent thermal and mechanical properties, as well as good oxidation resistance and alkaline stability, which can meet the application requirements of AEMs for fuel cells, exhibiting their bright application prospects in fuel cells.     

Homologous flexible multi-cationic cross-linkers modified poly(aryl ether sulfone) anion exchange membranes for fuel cell applications

Issues of unsatisfactory ionic conductivity and chemical stability should be solved for anion exchange membranes (AEMs) in practical fuel cell applications. A series of flexible spacers, homologous multi-cationic cross-linkers with different lengths, were designed and synthesized from 1,4-diazabicyclo(2.2.2)octane (DABCO) and 1,6-dibromohexane, and subsequently used to fabricate a series of flexible multi-cationic cross-linked poly(aryl ether sulfone) (CQPAES) AEMs. The CQPAES membranes fabricated by simultaneous cross-linking and membrane formation are tough and pliable. The length and number of cations of the cross-linkers show noticeable effects on the comprehensive membrane performance. The CQPAES membranes display more distinct nano-phase separation morphology and well-developed ion transfer channels due to the higher mobility and hydrophilicity of the flexible long-chain multi-cationic segments. As a result, the CQPAES membranes exhibit gradually increased water uptake and ionic conductivity with the increase of cross-linker length. Furthermore, DABCO and hexyl segments in the cross-linker greatly enhance the steric hindrance and electron cloud density of the quaternary ammonium groups, which inhibit the Hoffmann elimination reaction. Consequently, the CQPAES membranes display a significant improvement in alkali stability than conventional benzyl-substituted quaternary ammonium group type AEMs.     

Novel quaternized carbon dots modified polysulfone-based anion exchange membranes with improved performance

At present, low conductivity and poor chemical stability are still the biggest challenges in the research on anion exchange membranes (AEMs). Herein, novel nanocomposite AEMs were first constructed by introducing quaternized carbon dots (QCDs) into the imidized polysulfone matrix (Im-PSU). QCDs were synthesized by quaternization of CDs derived from citric acid and ethylenediamine. The physicochemical properties and electrochemical properties of the nanocomposite AEMs were significantly improved due to the introduction of QCDs. It was found that the QCDs can improve the ion transport channel of the nanocomposite AEMs. Compared with pure Im-PSU AEM, the OH⁻ conductivity and physicochemical properties of the nanocomposite membranes were enhanced, and the OH⁻ conductivity of ImPSU-1.0%-QCDs composite membrane can reach 109.3 mS cm⁻¹ at 80 °C, and 61.2% initial OH⁻ conductivity was maintained in 1.0 M NaOH solution for 500 h at 60 °C. Our research proves that the nanofiller with a small size can better improve the performance of composite AEMs, and provide an efficient strategy for future research work in the design and preparation of AEMs.     

Fabrication and characterization of poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) proton-conducting composite membranes for direct methanol fuel cells

A high performance poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) (PVA/MMT/PSSA) proton-conducting composite membrane was fabricated by a solution casting method. The characteristic properties of these blend composite membranes were investigated by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, methanol permeability measurement, and the AC impedance method. The ionic conductivities for the composite membranes are in the order of 10⁻³ S cm⁻¹ at ambient temperature. There are two proton sources used on this novel composite membrane: the modified MMT fillers and PSSA polymer, both materials all contain the -SO₃H group. Therefore, the ionic conductivity was greatly enhanced. The methanol permeabilities of PVA/MMT/PSSA composite membranes is of the order of 10⁻⁷ cm² s⁻¹. It is due to the excellent methanol barrier properties of the PVA polymer. The peak power densities of the air-breathing direct methanol fuel cells (DMFCs) with 1M, 2M, 4M CH₃OH fuels were 14.22, 20.00, and 13.09 mW cm⁻², respectively, at ambient conditions. The direct methanol fuel cell with this composite polymer membrane exhibited good electrochemical performance. The proposed PVA/MMT/PSSA composite membrane is therefore a potential candidate for future applications in DMFC.     

Quantifying water transport in anion exchange membrane fuel cells

Sufficient water transport through the membrane is necessary for a well-performing anion exchange membrane fuel cell (AEMFC). In this study, the water flux through a membrane electrode assembly (MEA), using a Tokuyama A201 membrane, is quantified using humidity sensors at the in- and outlet on both sides of the MEA. Experiments performed in humidified inert gas at both sides of the MEA or with liquid water at one side shows that the aggregation state of water has a large impact on the transport properties. The water fluxes are shown to be approximately three times larger for a membrane in contact with liquid water compared to vaporous. Further, the flux during fuel cell operation is investigated and shows that the transport rate of water in the membrane is affected by an applied current. The water vapor content increases on both the anode and cathode side of the AEMFC for all investigated current densities. Through modeling, an apparent water drag coefficient is determined to −0.64, indicating that the current-induced transport of water occurs in the opposite direction to the transport of hydroxide ions. These results implicate that flooding, on one or both electrodes, is a larger concern than dry-out in an AEMFC.     

Semi-interpenetrating network based on cross-linked poly(vinyl alcohol) and poly(styrene sulfonic acid-co-maleic anhydride) as proton exchange fuel cell membranes

A series of promising proton conducting membranes have been synthesized by using poly(vinyl alcohol), with sulfosuccinic acid (SSA) as a cross-linking agent and poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) as proton source, which form a semi-interpenetrating network (semi-IPN) PVA/SSA/PSSA-MA membrane. A bridge of SSA between PVA molecules not only reinforces the network but also provides extra proton conducting paths. PSSA-MA chains trapped in the network were the major sources of protons in the membrane. FT-IR spectra confirmed the success of the cross-linking reaction and molecular interactions between PVA and PSSA-MA. Associated characteristics of a proton conducting membrane including ion-exchange capacity (IEC), proton conductivity and water uptake were investigated. The measured IECs of the membranes increased with increase of PSSA-MA content varying from 20 to 80% and correlated well with the measured uptake water and proton conductivity. The semi-IPN membranes with PSSA-MA over 60% exhibited a higher proton conductivity than Nafion-115 and also a reasonable level of water uptake. Fuel cell performance of membrane electrode assemblies (MEA) was evaluated at various temperatures with H₂/air as well as H₂/O₂ gases under ambient pressure. A power density of 0.7 W cm⁻² was obtained for the MEA using PVA/SSA20/PSSA-MA80 membrane using H₂/O₂ at 50 °C.