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1.
It was reported that the existence of N-spirocyclic quaternary ammonium (QA) cation could improve alkaline stability of anion exchange membrane materials (AEM). Therefore, the cyclo-quaternization reaction with pyrrolidine (Pyr) and piperidine (Pip) was carried out to prepare quaternized poly (ether ether ketone)s bearing five-membered and six-membered N-spirocyclic quaternary ammonium (QA) groups in the phenyl side chains (QPEEK-spiro-pyr and QPEEK-spiro-pip), respectively. From the transmission electron microscope, the hydrophilic-hydrophobic phase-separated morphology was formed in QPEEK-spiro membranes after incorporating N-spirocyclic QA cations and bulky spacer simultaneously in the phenyl side chain. The effect of N-spirocyclic QA groups on performance of resulted AEMs was then studied in detail. The anion conductivities of QPEEK-spiro-pyr and QPEEK-spiro-pip in OH? form at 80 °C were 49.6 and 30.9 S cm?1, respectively. The remaining proportions of hydroxide conductivity for QPEEK-spiro-pyr and QPEEK-spiro-pip membranes after immersing in 1 M NaOH at 60 °C were 81.0% and 74.7%, respectively, which were higher than that of 62.3% for QPEEK-TMA containing conventional QA groups in the phenyl side chain. Fuel cell assembled with QPEEK-spiro-pyr achieves a peak power density of 90 mW cm?2. These results indicate the strategy of simultaneously introducing N-spirocyclic QA cations and bulky spacers can improve the performance of AEM to a certain extent. There are some other factors that influence the alkaline stability of the prepared AEMs, such as the existence of ether bonds in the main chain. However, this work still provides a valuable reference towards the molecular design of AEMs with improved performance.  相似文献   

2.
In this work, an effective design strategy for anion exchange membranes (AEMs) incorporating ether-bond free and piperidinium cationic groups promote chemical stability. A series of poly (isatin-piperidium-terphenyl) based AEMs were synthesized by superacid catalyzed polymerization reaction, followed by quaternization. The effect of functionalization on the performance of poly (isatin-N-dimethyl piperidinium triphenyl) (PIDPT-x) AEMs was investigated. Highly reactive N-propargylisatin was introduced into the backbone to achieve high molecular weight polymers (ηa = 2.06–3.02 dL g1) leading to robust mechanical properties, as well as modulating 1.78–2.00 mmol g−1 of the ion exchange capacity (IEC) of the AEMs by feeding. Apart from that, the rigid non-ionized isatin-terphenyl segment provides AEMs improved dimensional stability with a swelling ratio of less than 12% at 80 °C. Among them, PIDPT-90 exhibited a higher OH conductivity of 105.6 mS cm−1 at 80 °C. The alkali-stabilized PIDPT-85 AEM was presented, in which OH conductivity retention maintained 85.6% in a 2 M NaOH at 80 °C after 1632 h. Afterward, the direct borohydride fuel cells (DBFC) with PIDPT-90 membrane as a separator showed an open-circuit voltage of 1.63 V and a peak power density of 75.5 mWcm−2 at 20 °C. This work demonstrates the potential of poly (isatin- N-dimethyl piperidinium triphenyl) as AEM for fuel cells.  相似文献   

3.
Anion exchange membranes (AEMs) have emerged as crucial functional materials in various electrochemical device, such as fuel cell. Both the mechanical property and ionic conductivity play important roles in AEMs. Herein, a series of semi-interpenetrating polymer network AEMs are prepared by introducing flexible polyvinyl alcohol to the rigid photo-crosslinked poly (2,6-dimethyl-1,4-phenylene oxide) network. Such strategy endows AEM with tunable composition and mechanical property. Among these AEMs, membrane with an IEC of 1.46 mmol/g shows the highest mechanical strength of 30.8 MPa and a relatively lower swelling ratio, as well as the highest hydroxide conductivity. Importantly, the alkaline stability of these AEMs has been improved, 66.5% of the hydroxide conductivity is maintained after treatment in 1 M NaOH at 80 °C for 1000 h. Tentative assembly of H2/O2 fuel cell at 60 °C with this AEM displays a peak power density of 78 mW/cm2. All the results demonstrate that sIPN structure is a promising way to enhance the mechanical property, ionic conductivity, and the alkaline stability of AEMs for the future application in AEMFCs.  相似文献   

4.
A novel benzonorbornadiene derivative (BenzoNBD-Bis(Im+Br-Im+I)) grafted by multi-imidazolium cations side-chains combined the rigid alkyl spacer and flexible alkoxy spacer is designed and synthesized. Then, the BenzoNBD-Bis(Im+Br-Im+I) monomer is copolymerized with the epoxy functionalized norbornene monomer (NB-MGE) and norbornene (NB) via ring-opening metathesis polymerization (ROMP) using Grubbs 3rd catalyst. All as-designed triblock copolymer membranes (TBCMs) show a thermal decomposition temperature beyond 310 °C and can well be dissolved in common organic solvents. The self-cross-linked structure of anion exchange membrane (AEM) is confirmed by gel fraction and tensile measurement. The water uptake and swelling ratio of TBCMs and AEMs are also measured. Major properties required for AEMs such as ion exchange capacity (IEC), hydroxide conductivity and alkaline stability are investigated. AEM-9.09 shows a hydroxide conductivity of 100.74 mS cm−1 at 80 °C. Besides, the micro-phase separated morphology of AEM is confirmed by TEM, AFM and SAXS analyses, AEMs formed distinct micro-phase separation. The as-prepared AEM exhibits a peak power density of 174.5 mW cm−2 at 365.1 mA cm−2 tested in a H2/O2 single-cell anion exchange membrane fuel cell (AEMFC) at 60 °C. The newly developed strategy of self-cross-linked multi-imidazolium cations long side-chains triblock benzonorbornadiene copolymer provides an effective method to develop high-performance AEMs.  相似文献   

5.
Crosslinking is a valid approach to enhance the mechanical and durability performance of anion exchange membranes (AEMs). Herein, a facile and effective self-crosslinking strategy, with no need for an additional crosslinker or a catalyzer, is proposed. A series of tunable self-crosslinking and ion conduction polynorbornene membranes are designed. The 5-norbornene-2-methylene glycidyl ether (NB-MGE) component which affords self-crosslinking enhances dimensional stability, while the flexible 5-norbornene-2-alkoxy-1-hexyl-3-methyl imidazolium chloride (NB-O-Im+Cl) hydrophilic unit contributes high conductivity. The crosslinking significantly decreases the water uptake, and water swelling ratio provides excellent solvent-resistance and enhances the thermal and mechanical properties. Additionally, crosslinked rPNB-O-Im-x AEMs exhibit desirable alkaline stability. Impressively, the rPNB-O-Im-30 (IEC = 1.377) shows a moderate ion conductivity (61.8 m S cm−1, 80 °C), with a suppressed water absorption and 88.17% initial OH conductivity is maintained after treated for 240 h with a 1.0 M NaOH solution at 60 °C. Suitably assessed of rPNB-O-Im-30 AEM reveals a 98.4 mW cm−2 peak power density reached at a current density of about 208 mA cm−2. The report offers a facile and effectual preparative technique for preparing dimensional and alkaline stable AEMs for fuel cells applications.  相似文献   

6.
Alkaline anion exchange membrane fuel cell has fast cathode reactions and thus allows the use of low cost electrocatalysts. However, its practical application is hindered by the low hydroxide ion conductivity and alkaline stability of AEM. In this study, pendent piperidinium functionalized polyetheretherketone is synthesized and blended with polybenzimidazole for fabrication of composite anion exchange membrane. The pendent piperidinium functionalized side chains can create well-connected ionic transporting channels and thus impart the blend membranes high hydroxide conductivity (61.5–72.8 mS cm−1 at 80 °C) and good tensile strength (42.8–58.9 MPa). Due to the strong interactions between polybenzimidazole and piperidinium groups of the polymers as confirmed by Fourier transform infrared spectroscopy, the piperidinium functionalized blend anion exchange membrane can retain 95% of its original OH conductivity value when treated in 1 M KOH at 60 °C for 576 h. The single fuel cell assembled with the membrane can yield a peak power density of 87 mW cm−2 at 80 °C. Our work provides a new and effective method to balance the hydroxide conductivity and alkaline stability of anion exchange membranes.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
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.  相似文献   

11.
High hydroxide conductivity and good stability of anion exchange membranes (AEMs) is the guarantee that anion exchange membrane fuel cells (AEMFCs) yield high power output for a long time. Balanced conductivity and stability can be better guaranteed by adopting a relatively low ion exchange capacity (IEC) while reducing the ion transport resistance Herein, a novel block copolymer AEM was designed and synthesized, which contains hydrophobic polymer of intrinsic microporosity (PIM) blocks and hydrophilic, quaternized polysulfone (PSF) blocks. The PIM block imparts high free volume to the membrane so that the resistance of hydroxide ion transport can be reduced; meanwhile, the hydrophilic block can self-assemble more easily to produce a better developed hydrophilic microphase, which may function as efficient channels for hydroxide ion transport. Both transmission electron microscopy images and small-angle X-ray scattering patterns suggested that the resulting AEM possessed a microphase separated morphology. The membrane showed a conductivity of 52.6 mS cm-l at 80 °C with a relatively low IEC of 0.91 mmol g?1. It also exhibited a good dimensional stability, swelling ratio maintained almost constant (ca. 17%) at 25 to 80 °C. The assembled H2/O2 fuel cell yielded a peak power density of 270 mW cm?2 at 560 mA cm?2. Our work demonstrates that incorporation of PIM in an AEM by means of block polymerization is an efficient way of promoting microphase separation and facilitating ion transport.  相似文献   

12.
A kind of anion exchange membranes (AEMs) with CC bond end-group crosslinked structure was synthesized successfully. Unlike the traditional aliphatic AEMs, the AEMs were prepared in this work by a strategy to realize the CC bond thermal end-group crosslinking reaction, exhibiting an obvious microphase separation structure and a suitable dimensional stability. The well-defined ion channels constructed in the AEMs guarantee the fast OH conduction, as confirmed via physical and chemical characterization. The conductivity was dramatically enhanced due to the effective ion channels and increased ion exchange capacity. Among the as-prepared AEMs, the PHFB-VBC-DQ-80% AEM has a conductivity of 135.80 mS cm−1 at 80 °C. The single cell based on PHFB-VBC-DQ-80% can achieve a power density of 141.7 mW cm−2 at a current density of 260 mA cm−2 at 80 °C. The AEMs show good thermal stability verified by a thermogravimetric analyzer (TGA). Furthermore, the ionic conductivity of PHFB-VBC-DQ-80% only decreased by 7.1% after being soaked in a 2 M NaOH solution at 80 °C for 500 h.  相似文献   

13.
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.  相似文献   

14.
SEBS (styrene-b-(ethylene-co-butylene)-b-styrene)) is a non-aryl-ether-type tri-block copolymer widely used as an anion exchange membrane (AEM) material due to its excellent alkaline stability and phase separation properties. However, low tensile strength due to the aliphatic chains and the poor physical properties of the SEBS-based membranes limit their practical application for AEM water electrolysis (AEMWE) or AEM fuel cell (AEMFC). In this study, three types of crosslinked AEMs were prepared using bromohexyl pentafluorobenzyl SEBS as a polymer backbone, and three different crosslinkers, dimethyl amine (DMA), tetramethyl diaminohexane (TMHA), and tris(dimethyl aminomethyl) phenol (TDMAP). Once introduced, these crosslinking agents were converted into the corresponding conducting head groups. The thermal, chemical, physical, and electrical properties of the obtained crosslinked membranes were then investigated for use in AEMWE. In particular, the TDMAP-50x-SEBS membrane with 50% degree of crosslinking experienced hydrogen bonding with water and OH due to the presence of OH groups in the structure of the crosslinking agent (TDMAP). Because of this, the membrane showed an improved morphology and high conductivity (20 °C: 31.8 mS cm−1, 80 °C: 109.9 mS cm−1). In addition, TDMAP induced physical crosslinking by hydrogen bonding between molecules so that the corresponding membrane (TDMAP-50x-SEBS) exhibited high alkaline and oxidative stability and good mechanical properties. This SEBS-based membrane has a tensile strength of 18.0 MPa and Young's modulus of 165.14 MPa. The WE single-cell test (1 M KOH solution at 70 °C) using TDMAP-50x-SEBS also showed a cell performance of 1190 mA cm−2 at 2.0 V. This is 126% higher than the cell performance measured for FAA-3-50, a commercialized AEM material, under the same conditions.  相似文献   

15.
In recent years, ether-free polyaryl polymers prepared by superacid-catalyzed Friedel-Crafts polymerization have attracted great research interest in the development of anion exchange membranes(AEMs) due to their high alkali resistance and simple synthesis methods. However, the selection of monomers for high-performance polymer backbone and the relationship between polymer structure construction and properties need further investigated. Herein, a series of free-ether poly(aryl piperidinium) (PAP) with different polymer backbone steric construction were synthesized as stable anion exchange membranes. Meta-terphenyl, p-terphenyl and diphenyl-terphenyl copolymer were chosen as monomers to regulate the spatial arrangement of the polymer backbone, which tethered with stable piperidinium cation to improve the chemical stability. In addition, a multi-cation crosslinking strategy has been applied to improve ion conductivity and mechanical stability of AEMs, and further compared with the performance of uncrosslinked AEMs. The properties of the resulting AEMs were investigated and correlated with their polymer structure. In particular, m-terphenyl based AEMs exhibited better dimensional stability and the highest hydroxide conductivity of 144.2 mS/cm at 80 °C than other membranes, which can be attributed to their advantages of polymer backbone arrangement. Furthermore, the hydroxide conductivity of the prepared AEMs remains 80%–90% after treated by 2 M NaOH for 1600 h, exhibiting excellent alkaline stability. The single cell test of m-PTP-20Q4 exhibits a maximum power density of 239 mW/cm2 at 80 °C. Hence, the results may guide the selection of polymer monomers to improve performance and alkaline durability for anion exchange membranes.  相似文献   

16.
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.  相似文献   

17.
Herein, poly (phenylene) oxide (PPO)-based cross-linked anion exchange membranes (AEMs) with flexible, long-chain, bis-imidazolium cation cross-linkers are designed and synthesized. Although the cross-linked membranes possess high ion exchange capacity (IEC) values of up to 3.51–3.94 meq g−1, they have a low swelling degree and good mechanical strength because of their cross-linked structure. Though the membranes with the longest flexible bis-imidazolium cation cross-linker (BMImH-PPO) possess the lowest IEC among these PPO-based AEMs, they show the highest conductivity (24.10 mS cm−1 at 20 °C) and highest power density (325.7 mW cm−2 at 60 °C) because of the wide hydrophilic/hydrophobic microphase separation in the membranes that promote the construction of ion transport channels, as confirmed by atom force microscope (AFM) images and the small angle X-ray scattering (SAXS) analyses. Furthermore, the BMImH-PPO samples exhibit good chemical stability (10% and 6% decrease in IEC and conductivity, respectively, in 2 M KOH at 80 °C for 480 h, and a 22% decrease in weight in Fenton's reagent at 60 °C for 120 h), making such cross-linked AEMs potentially applicable in alkaline anion exchange membrane fuel cells.  相似文献   

18.
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.  相似文献   

19.
Anion exchange membranes (AEMs) with higher ion exchange capacities (IECw) are limited to applications due to excessive swelling and higher water uptake. Crosslinked macromolecular structures have been a strategy to balance between ionic conductivity and swelling in membranes. However, highly crosslinked AEMs are usually mechanically brittle and poorer in ion transport. Thus we report a series of partially diamine crosslinked (X = 10%, 15%, 20%) comb-shaped AEMs functionalized with dimethylhexadecylammonium groups exhibiting improved flexibility, water uptake and swelling properties over conventional un-crosslinked or fully crosslinked materials. The higher conductivities in these PPO AEM(X) (for example, X = 20%, IECw = 1.96 mmol/g, σ(OH) ~ 67 mS/cm at 80 °C) are attributed to the distinct nanophase separation as observed in SAXS and AFM analyses. Finally, the microbial fuel cell performances of the membranes were compared with commercially available cation and anion exchange membranes.  相似文献   

20.
The main issues facing the development of Anion Exchange Membranes (AEM) are the low hydroxide ion (OH) conductivity compared to protons (H+), and the thermal and chemical stability. Based on the its unique two-dimensional structure, graphene is estimated to be one of the best solutions for the hydrogen ions (H+ and OH) selectivity and conductivity improvement. This work presents the graphene-composite membranes (AEMGrs) preparation and characterization in comparison with commercial FAA3-20® and FAA3-30® membranes from Fumatech. Various amounts of commercial graphene were incorporated into the Fumion® FAA-3 in NMP (10%), solutions which were then used to fabricate new AEMs by the Doctor-Blade (DB) method. Commercial and graphene-composite AEMs were studied by infrared spectroscopy with Fourier Transformation (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), water uptake (WU), ion exchange capacity (IEC), and in plane four-points electrochemical impedance spectroscopy (4p-EIS). The results indicated that the composite membranes containing 50 mg of graphene exhibited an improved IEC (3.16 mmol g−1) and OH conductivity (113.27 mS cm−1) at 80 °C measured in 0.01 M KOH (pH = 12).  相似文献   

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