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.     

Synthesis and characterization of long-side-chain type quaternary ammonium-functionalized poly (ether ether ketone) anion exchange membranes

A series of quaternary ammonium salt poly(ether ether ketone) AEMs containing long ether substituents are successfully prepared, and their chemical structure is confirmed by ¹H NMR and FT-IR. The distinct microphase separation morphology of AEMs is observed by TEM. As the content of methylhydroquinone increases, the ion conductivity of AEMs gradually increases. When the content of methylhydroquinone increases to 80%, the hydroxide conductivity of PEEK-DABDA-80 membrane reaches 0.052 S/cm at 80 °C. Meanwhile, it exhibits excellent mechanical properties and anti-swelling ability, with tensile strength of 25 MPa, elongation at break of 8.12% and swelling ratio is only 17.4% at 80 °C. And AEMs also display the better thermal stability. After soaked in 1 M NaOH at 60 °C for 30 days, PEEK-DABDA-80 membrane shows acceptable ion conductivity of 0.021 S/cm at 60 °C. In view of these properties, PEEK-DABDA-x AEMs may display potential application as alkaline AEMs.     

Fluorene-containing poly(arylene ether sulfone nitrile)s multiblock copolymers as anion exchange membranes

A series of novel fluorene-containing poly(arylene ether sulfone nitrile)s (FPESN-m/n) multiblock copolymers bearing 1,2-dimethylimidazole groups (ImFPESN-m/n) were synthesized for preparing anion exchange membranes (AEMs). Bromination rather than chloromethylation was used in this work. The bulky and rigid fluorene groups were introduced to force each chain apart to create large interchain spacing. Strong polar nitrile groups were introduced into the hydrophobic segments with the intention of enhancing the anti-swelling property of the AEMs. The length of fluorene–containing hydrophobic segment was varied to study the structure–property of the AEMs. With the ion groups anchored selectively and densely on the hydrophilic segments, all the AEMs exhibited well-defined hydrophilic/hydrophobic microphase-separated structures. As a result, the AEMs showed high hydroxide conductivities in the range of 35.2–118.3 mS cm⁻¹ from 30 to 80 °C and superb ratios of ionic conductivity to swelling at 80 °C. Furthermore, the AEMs also exhibited good mechanical properties, thermal and alkaline stabilities.     

Branched poly(ether ether ketone) based anion exchange membrane for H2/O2 fuel cell

High-performance anion exchange membranes (AEMs) are in need for practical application of AEM fuel cells. Novel branched poly(ether ether ketone) (BPEEK) based AEMs were prepared by the copolymerization of phloroglucinol, methylhydroquinone and 4,4′-difluorobenzophenone and following functionalization. The effects of the branched polymer structures and functional groups on the membrane's properties were investigated. The swelling ratios of all the membranes were kept below 15% at room temperature and had good dimensional stability at elevated temperatures. The branching degree has almost no effect on the dimensional change, but plays a great role in tuning the nanophase separation structure. The cyclic ammonium functionalized membrane showed a lower conductivity but a much better stability than imidazolium one. The BPEEK-3-Pip-53 membrane with the branching degree of 3% and piperidine functionalization degree of 53% showed the best performances. The ionic conductivity was 43 mS cm⁻¹ at 60 °C. The ionic conductivity in 1 M KOH at 60 °C after 336 h was 75% of its initial value (25% loss of conductivity), and the IEC was 83% of its initial value (17% loss of IEC), suggesting good alkaline stability. The peak energy density (60 °C) of the single H₂/O₂ fuel cell with BPEEK-3-Pip-53 membrane reached 133 mW cm⁻² at 260 mA cm⁻².     

Novel poly(carbazole-butanedione) anion exchange membranes constructed by obvious microphase separation for fuel cells

To develop anion exchange membranes with excellent chemical stability and high performance. A series of quaternary ammonium functionalized (hydrophilic) hydrophobic rigid poly (carbazole-butanedione) (HOCB-TMA-x) anion exchange membranes were prepared, where x represents the percentage content of hydrophobic unit octylcarbazole (OCB). Due to the introduction of hydrophobic rigid unit octylcarbazole and hexyl flexible side chain, the hydrophilic-hydrophobic microstructure of AEMs was developed. The AEMs exhibit excellent overall performance, specifically the low swelling ratio HOCB-TMA-30 membrane exhibits the highest OH^? conductivity of 152.9 mS/cm at 80 °C. Furthermore, the ionic conductivity of AEM decreased by only 9.5% after 2250 h of immersion in 1 M NaOH. The maximum peak power density of a single cell with a current density of 4.38 A/cm² at 80 °C was 1.85 W/cm².     

High alkaline stability and long-term durability of imidazole functionalized poly(ether ether ketone) by incorporating graphene oxide/metal-organic framework complex

The poly(ether ether ketone) (PEEK) was prepared as organic matrix. ZIF-8 and GO/ZIF-8 were used as fillers. A series of novel new anion exchange membranes (AEMs) were fabricated with imidazole functionalized PEEK and GO/ZIF-8. The structure of ZIF-8, GO/ZIF-8 and polymers are verified by ¹H NMR, FT-IR and SEM. This series of hybrid membranes showed good thermal stability, mechanical properties and alkaline stability. The ionic conductivities of hybrid membranes are in the range of 39.38 mS cm^?1–43.64 mS cm^?1 at 30 °C, 100% RH and 59.21 mS cm^?1–86.87 mS cm^?1 at 80 °C, 100% RH, respectively. Im-PEEK/GO/ZIF-8-1% which means the mass percent of GO/ZIF-8 compound in Im-PEEK polymers is 1%, showed the higher ionic conductivity of 86.87 mS cm^?1 at 80 °C and tensile strength (38.21 MPa) than that of pure membrane (59.21 mS cm^?1 at 80 °C and 19.47 MPa). After alkaline treatment (in 2 M NaOH solution at 60 °C for 400 h), the ionic conductivity of Im-PEEK/GO/ZIF-8-1% could also maintain 92.01% of the original ionic conductivity. The results show that hybrid membranes possess the ability to coordinate trade-off effect between ionic conductivity and alkaline stability of anion exchange membranes. The excellent performances make this series of hybrid membranes become good candidate for application as AEMs in fuel cells.     

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.     

Highly alkaline stable fully-interpenetrating network poly(styrene-co-4-vinyl pyridine)/polyquaternium-10 anion exchange membrane without aryl ether linkages

To avoid the detrimental effect of aryl ethers on the alkali stability of anion exchange membrane (AEM), elaborately designed and synthesized poly(styrene-co-4-vinyl pyridine) (PS4VP) copolymer without aryl ether linkages is used to prepare AEMs. By introducing commercialized polyquaternium-10 (PQ-10) as the main ion-conducting molecule, the fully-interpenetrating polymer network quaternized PS4VP/PQ-10 (F-IPN QPS4VP/PQ-10) AEMs are prepared by cross-linking PS4VP and PQ-10, respectively. The as-prepared F-IPN QPS4VP/PQ-10 AEMs have obvious nanoscale microphase-separated morphologies, which ensure the membranes have good mechanical properties and dimensional stability. With optimized component ratios, F-IPN QPS4VP/PQ-10 AEM exhibits high ionic conductivity (74.29 mS/cm at 80 °C) and power density (111.83 mW/cm² at 60 °C), as well as excellent chemical stabilities (94.36% retaining of initial mass after immersion in Fenton reagent at 30 °C for 10 days, and 92.28% retaining of original ionic conductivity after immersion in 1 M NaOH solution at 60 °C for 30 days), which are greater than those of semi-interpenetrating polymer network QPS4VP/PQ-10 AEM. In summary, a combination of fully-interpenetrating polymer network and stable polymer chains and ion-conducting moieties is found to effectively overcome the trade-off between high ionic conductivity and good dimensional/chemical stabilities.     

Comb-shaped fluorene-based poly(arylene ether sulfone nitrile) as anion exchange membrane

A series of comb-shaped fluorene-based poly (arylene ether sulfone nitrile) (CFPESN–x) was synthesized as anion exchange membranes (AEMs). The well-designed architecture of fluorene-based main chains and comb-shaped C8 long alkyl side chains containing quaternary ammonium groups was responsible for the clear microphase-separated morphologies, as confirmed by small angle X-ray scattering and atomic force microscopy. Moreover, nitrile groups on main chains also showed a profound influence on membrane morphology and properties. CFPESN–x exhibited more interconnected ionic domains with increasing the nitrile group content resulting in higher conductivities and anti-swelling property. Then CFPESN–x exhibited high ionic conductivities in the range of 27.1–91.5 mS cm⁻¹ from 30 to 80 °C and superior ratios of conductivity to swelling ratio at 80 °C at moderate IECs. Moreover, CFPESN–x also showed good mechanical properties and thermal stability, and optimizable alkaline stability and single cell performance.     

Block poly(arylene ether nitrile ketone)s with comb-shaped alkyl chains as anion exchange membranes

A new approach is presented here for constructing higher-performance anion exchange membranes (AEMs) by combining block-type and comb-shaped architectures. A series of quaternization fluorene-containing block poly (arylene ether nitrile ketone)s (QFPENK-m-n) were synthesized by varying the length of hydrophobic segment as AEMs. The well-designed architecture, which involved grafting comb-shaped C10 long alkyl side chains onto the block-type main chains, formed efficient ion-transport channels, as confirmed by atomic force microscopy. As a result, the AEMs showed high hydroxide conductivities in the range of 34.3–102.1 mS⋅cm⁻¹ from 30 to 80 °C at moderate ion exchange capacities (IECs). Moreover, the hydrophobic segment with nitrile groups also exhibited a profound anti-swelling property for the AEMs, resulting in ultralow swelling ratios ranging from 4.7% to 7.1% at 30 °C and 7.5%–9.8% at 80 °C, as well as superb conductivity-to-swelling ratios at 80 °C. In addition, the AEMs displayed good mechanical properties, thermal and oxidative stability, and optimizable alkaline stability.     

Quaternary ammonium-functionalized hexyl bis(quaternary ammonium)-mediated partially crosslinked SEBSs as highly conductive and stable anion exchange membranes

We chemically modify a commercially available elastomeric triblock copolymer, poly(styrene-b-ethylene-co-butylene-b-styrene) SEBS, to produce quaternary ammonium-functionalized hexyl bis(quaternary ammonium)-mediated partially-crosslinked SEBSs with different grafting degree of the conducting head groups as highly conductive and stable anion exchange membranes (AEMs). In an attempt to achieve a high ion exchange capacity and hence conductivity of the corresponding membranes without causing ‘gelation’, which these types of SEBS polymers typically experience, we use a SEBS with a high content (57%) of styrene, and graft the quaternary ammonium (QA) as both a crosslinker and the conducting head group on the side chain of the SEBS. The partial crosslinking approach, in combination with introducing these QA-conducting head groups as the side chain of the SEBS, helps to form larger ion clusters, and also to form a nano-phase morphology with long-range connecting channels. This induced the highest ion conductivity, 174.8 mS cm⁻¹ at 80 °C, reported to date among these types of SEBS series. In addition, we obtain excellent cell performance with a current density of 450 mA cm⁻² at 0.6 V and a peak power density of 315 mW cm⁻² at 95% RH and 60 °C using the corresponding AEM.     

A facile,effective thermal crosslinking to balance stability and proton conduction for proton exchange membranes based on blend sulfonated poly(ether ether ketone)/sulfonated poly(arylene ether sulfone)

The development of hydrocarbon polymer electrolyte membranes with high proton conductivities and good stability as alternatives to perfluorosulfonic acid membranes is an ongoing research effort. A facile and effective thermal crosslinking method was carried out on the blended sulfonated poly (ether ether ketone)/poly (aryl ether sulfone) (SPEEK/SPAES) system. Two SPEEK polymers with ion exchange capacities (IECs) of 1.6 and 2.0 mmol g^?1 and one SPAES polymer (2.0 mmol g^?1) were selected to create different blends. The effect of thermal crosslinking on the fundamental properties of the membranes, especially their physicochemical stability and electrochemical performance, were investigated in detail. The homogeneous and flexible thermally-crosslinked SPEEK/SPAES membranes displayed excellent mechanical toughness (27–46 Mpa), suitable water uptake (<60%), high dimensional stability (swelling ratio < 15%) and large proton conductivity (>120 mS cm^?1) at 80 °C. The thermal crosslinking membranes also show significantly enhanced hydrolytic (<2.5%) and oxidative stability (<2%). Fuel cell with t-SPEEK/SPAES (1:2:2) membrane achieves a power density of 665 mW cm^?2 at 80 °C.     

Preparation and characterization of a polyvinyl alcohol grafted bis-crown ether anion exchange membrane with high conductivity and strong alkali stability

A new type of symmetrical bis-crown ether is prepared by connecting dibenzo-18-crown-6 ether on both sides of the chromotropic acid, and then grafting the aforementioned bis-crown ether onto polyvinyl alcohol matrix to prepare a series of anion exchange membranes (AEMs), which their have high conductivity and strong alkali stability. These synthesized membranes were named B-C_X%-P AEMs (x is the mass percentage of the symmetrical bis-crown ether (B–C)). Then, the chemical structure of aforementioned AEMs were verified by means of ¹H NMR, FT-IR and UV. Meanwhile, the OH⁻ conductivity, alkaline stability and single cell performance of the synthesized membrane were also investigated. The results revealed that the conductivity of B–C_30%-P membrane is the highest at 80 °C (235 mS cm⁻¹), and the power density is also the highest (197 mW cm⁻²), and the alkali stability of the membrane synthesized in this paper was also improved. The conductivity at 80 °C was only reduced by 4%, which was obtained by immersing the B–C_30%-P membrane immersed in 6 mol L⁻¹ KOH solution for 168 h, which the aforementioned results proved that the synthesized membrane in this research had excellent OH⁻ conductivity and alkaline stability.     

Synthesizing spindle-shaped anion exchange membranes to improve conductivity and stability

High ionic conductivity and excellent alkaline stability are very important for solid electrolyte. Therefore, spindle-shaped anion exchange membranes (AEMs) based on poly (arylene ether ketone) and 1-Bromo-N,N,N-trimethylhexane-6-aminium bromide (Br-QA) have been prepared. The obtained Br-QA can be grafted with poly (arylene ether ketone) main chains to form micro-phase separation structure enhancing the ionic conductivity. Especially, the grafting quaternary ammonium (QA) cation groups are separated by alkyl bromine endows the AEMs with alkaline stability features. Simultaneously, the OH⁻ conductivity of the QA-PAEK-0.6 obtained membranes is 0.046 S/cm under fully hydrated conditions at 60 °C. After immersing into 1 M NaOH alkaline solution for 15 days at 60 °C, the anionic conductivity still high to 0.03 S/cm. Meanwhile, the poly (arylene ether ketone) backbones provide excellent mechanical properties and the Br-QA cation groups also possess good thermal stability, which satisfy the requirement of wide applications.     

Preparation and performance of bisimidazole cationic crosslinked addition-type polynorbornene-based anion exchange membrane

The late transition metal catalyst system (η³-allyl)Pd(PPh₃)Cl/Li[B(C₆F₅)₄]·2.5Et₂O (Li[FABA]) was used to catalyze 5-norbornene-2-methylenehexyl ether (NB-MHE) and 5-norbornene-2-methylene-(6-bromohexyl) ether (NB–O–Br) controllable addition copolymerization to obtain post-functionalized vinyl addition-type block copolymer aP(NB-O-Br-b-NB-MHE). 1,6-Bis(2-methylimidazole)hexane (Bis-MeIm) was used as a crosslinking agent to prepare a series of anion exchange membranes (AEMs) CL-aP(NB-O-Br-b-NB-MHE). The initial thermal decomposition temperature of the obtained addition-type polynorbornene-based AEM was about 250 °C. The AEM had moderate water uptake (WU) and swelling ratio (SR), and obvious micro-phase separation structure that could be observed from the AFM phase diagram. It could maintain high OH^? conductivity (85.07 mS cm^?1, 80 °C) and alkali resistance stability (soaking alkali for more than 500 h at 25 °C). In the single cell test of the H₂/O₂ fuel cell assembled by CL5-aP(NB-O-Br-b-NB-MHE), the peak power density was 177 mW cm^?2.     

Polyaryl piperidine anion exchange membranes with hydrophilic side chain

Recently, the development of high-performance and durable anion exchange membranes has been a top priority for anion exchange membrane fuel cells. Here, a series of polyaryl piperidine anion exchange membranes with hydrophilic side chain (qBPBA-80-OQ-x) are prepared by the superacid-catalyzed Friedel-Crafts reaction. AFM images show that the hydrophilic side chain and hydrophobic main chain form a distinct microphase separation structure. The AEMs of qBPBA-80-OQ-100 and qBPBA-80 have close mechanical strength, but the ionic conductivity of the former (81 mS/cm, 80 °C) is higher than the latter (73 mS/cm, 80 °C). In addition, qBPBA-80-OQ-100 AEM loses by 15.0% after an alkaline treatment of 720 h, while qBPBA-80 AEM loses by 17.8%. The results indicate that the introduction of hydrophilic side chain not only promotes the formation of microphase separation structure, but also improves the ionic conductivity and alkaline resistance of polyaryl piperidine AEMs.     

A novel quaternized poly(ether sulfone) membrane for alkaline fuel cell application

A new type of poly(ether sulfone)‐based self‐aggregated anion exchange membrane (AEM) was successfully synthesized and used in H₂/O₂ fuel cell applications. The self‐aggregated structural design improves the effective mobility of OH^? ion and increases the ionic conductivity of AEM. Proton nuclear magnetic resonance and Fourier transform infrared spectroscopy spectra confirm successful chloromethylation and quaternization in the poly(ether sulfone). Thermogravimetric analysis curves show the self‐aggregated membrane was thermally stable up to 180 °C. The AEM also has excellent mechanical properties, with tensile strength 53.5 MPa and elongation at break 47.6% under wet condition at room temperature. The performance of H₂/O₂ single fuel cell at 30 °C showed the maximum power density of 162 mW cm^?2. These results show that the self‐aggregated quaternized poly(ether sulfone) membrane is a potential candidate for alkaline fuel cell applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Increased microbial fuel cell performance using quaternized poly ether ether ketone anionic membrane electrolyte for electricity generation

A high-performance hydroxide exchange membrane was prepared by the chloromethylation and quaternization of Poly ether ether ketone (PEEK) for microbial fuel cell applications. The study reports on the synthesis of a novel quaternized poly ether ether ketone (QPEEK) membrane and subsequent utilization of the ionomer as an anion exchange membrane (AEM). The structural characterization of chloromethylation and quaternization of PEEK was confirmed by FT-IR and ₁H¹ NMR spectroscopy and the morphologies were viewed by scanning electron microscopy. The effects of oxygen crossover and specific substrate crossover on cathode potential were also studied in detail. The investigation of QPEEK with the commercially available AEM (AMI-7001) revealed that the QPEEK shows excellent static properties, i.e. ion-exchange capacity, water uptake, thickness, etc.; and kinetic properties, i.e. diffusion permeability and better durability over 250 days. Power density obtained from an MFC containing the QPEEK-AEM produced higher value (60 W/m³) than the commercial AMI-7001 AEM (52 W/m³). This study shows that QPEEK could be used as an efficient and a cost effective AEM for an MFC.     

Effects of hydrolysis degree on ion-doped anion exchange membranes in direct borohydride fuel cells

Herein, polyvinyl alcohol based anion exchange membranes (AEMs) doped with various cobalt and chloride salts are synthesized to investigate the structure-performance relationship of ion-doped AEMs systemically. The performances of ion-doped AEMs are found to be related to the hydrolysis degree (DH) of the doped anions and cations. It is found that cations with varying DH transformed into hydroxides with different sizes and dispersions, which plays a key role in determining the structures and properties of cation-doped AEMs. On the other hand, weak-acid anions remained in the AEMs after alkali immersion, hindering OH⁻ conduction and leading to the degradation of the anion-doped AEMs. High DH cations mildly react with the matrix and transform into more dispersive complexes, while low DH anions are replaced by OH⁻.The direct borohydride fuel cell using CuCl₂-doped AEM exhibits a maximum power density of 202.4 mW cm⁻² at 30 °C.     

Bis-pyridinium crosslinked poly(ether ether ketone) anion exchange membranes with enhancement of hydroxide conductivity and alkaline stability

A series of tunable bis-pyridinium crosslinked PEEK-BiPy-x anion exchange membranes (AEMs) are prepared successfully to improve the “trade-off” between ionic conductivity and alkaline stability. The crosslinking density of bis-pyridinium is optimized to promote microphase separation and guarantee the free volume. All the PEEK-BiPy-x membranes have a distinct microphase separation pattern observed by atomic force microscopy (AFM) and the PEEK-BiPy-x membranes also display adequate thermal, mechanical and dimensional stability. Impressively, the PEEK-BiPy-0.5 membrane exhibits maximum tensile strength (58.53 MPa) and highest IEC of 1.316 mmol·g^?1. Meanwhile, its hydroxide conductivity reaches up to 70.86 mS·cm^?1 at 80 °C. Besides, great alkaline stability of PEEK-BiPy-0.5 membrane is obtained with conductivity retention of 91.74% after 1440 h in 1 M NaOH solution, owing to the crosslinked structure of the AEMs and steric effect of bis-pyridinium cations. Overall, the PEEK-BiPy-x membranes possess potential applications in AEMs.