共查询到20条相似文献,搜索用时 281 毫秒
1.
Pei Chen Xinbing Chen Zhongwei An Kangcheng ChenKenichi Okamoto 《International Journal of Hydrogen Energy》2011,36(19):12406-12416
A series of crosslinkable sulfonated poly(arylene ether sulfone)s (SPAESs) were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil and 3,3′-disulfonated-4,4′-difluorodiphenyl sulfone disodium salt. Quinoxaline-based crosslinked SPAESs were prepared via the cyclocondensation reaction of benzil moieties in polymer chain with 3,3′-diaminobenzidine to form quinoxaline groups acting as covalent and acid-base ionic crosslinking. The uncrosslinked and crosslinked SPAES membranes showed high mechanical properties and the isotropic membrane swelling, while the later became insoluble in tested polar aprotic solvents. The crosslinking significantly improved the membrane performance, i.e., the crosslinked membranes had the lower membrane dimensional change, lower methanol permeability and higher oxidative stability than the corresponding precursor membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane (CS1-2) with measured ion exchange capacity of 1.53 mequiv. g−1 showed a reasonably high proton conductivity of 107 mS/cm with water uptake of 48 wt.% at 80 °C, and exhibited a low methanol permeability of 2.3 × 10−7 cm2 s−1 for 32 wt.% methanol solution at 25 °C. The crosslinked SPAES membranes have potential for PEFC and DMFCs. 相似文献
2.
《International Journal of Hydrogen Energy》2020,45(54):29738-29748
A series of sulfonated poly(arylene ether ketone sulfone)s polymer having a degree of sulfonation of 80% and a carboxyl group in the side chain (C-SPAEKS) were prepared by polycondensation. The 4-aminopyridine grafted sulfonated poly(arylene ether ketone sulfone)s polymer membranes (SPPs) were prepared by amidation reaction with the carboxyl group to immobilize 4-aminopyridine on the side chain. The 1H NMR results and Fourier transform infrared of SPP membranes demonstrated the successful grafting of the 4-aminopyridine. Proton conductivity, water absorption, swelling ratio, and thermal stability of different proportions of SPP membranes were investigated under the different conditions. With the increase of pyridine grafting content, the methanol permeability coefficient of the membrane decreased significantly from 8.17 × 10−7 cm2s−1 to 8.92 × 10−8 cm2s−1 at 25 °C. And, the proton conductivity and relative selectivity of the membrane were positively correlated with the grafted pyridine content. Among them, the SPP-4 membrane exhibited the highest proton conductivity of 0.088 Scm−1 at 100 °C. The relative selectivity increased from 4.73 × 104 S scm−3 to 9.84 × 104 S scm−3. 相似文献
3.
《International Journal of Hydrogen Energy》2019,44(12):6136-6147
In this work, the organic-inorganic hybrid membranes were prepared. The synthesis and properties of the hybrid membranes were investigated. The sulfonated poly(arylene ether ketone sulfone) containing amino groups (Am-SPAEKS) was synthesized by nucleophilic polycondensation. The sol-gel method was used to prepared functional titania inorganic particles (L-TiO2). The 1H NMR and FT-IR were performed to verified the structure of Am-SPAEKS and L-TiO2. The organic-inorganic hybrid membranes showed both good thermal stabilities and mechanical properties than that of Am-SPAEKS. The L-Am-15% membrane exhibited the highest Young's modulus (2262.71 MPa) and Yield stress (62.09 MPa). The distribution of L-TiO2 particles was revealed by SEM. Compared to Am-SPAEKS, the hybrid membranes showed higher proton conductivities. The L-Am-15% exhibited the highest proton conductivity of 0.0879 S cm−1 at 90 °C. The results indicate that the organic-inorganic hybrid membranes have potential for application in proton exchange membrane fuel cells. 相似文献
4.
《International Journal of Hydrogen Energy》2020,45(51):27527-27538
In this study, phosphotungstic acid-encapsulated MIL-101 (Fe) (HPW@MIL-100 (Fe)) was synthesized by the in-situ direct hydrothermal method. Due to the large mesoporous cages and small microporous windows of MIL-100 (Fe), HPW could be well loaded and confined in the cages of MIL-100 (Fe). Furthermore, novel hybrid proton exchange membranes were fabricated by incorporating HPW@MIL-100 (Fe) into sulfonated poly (arylene ether ketone sulfone) containing carboxyl groups (C-SPAEKS) matrix. The structures of MIL-100 (Fe), HPW@MIL-100 (Fe), C-SPAEKS, and hybrid membranes were characterized by XRD and FT-IR. The HPW@MIL-100 (Fe), with a large amount of phosphotungstic acid in cages, could enhance the proton conductivities of hybrid membranes. The hybrid membrane with 4% content of HPW@MIL-100 (Fe) achieved a high proton conductivity of 0.072 S cm−1 at 80 °C and 100% relative humidity, which was 1.8 times higher than that of pure C-SPAEKS (0.040 S cm−1) at the same conditions. Meanwhile, the introduced HPW@MIL-100 (Fe) fillers improved the dimensional stability of hybrid membranes. These results indicate that introduction of MIL-100 (Fe) materials loaded with HPW plays an important role in improving the comprehensive performance and this series of hybrid membranes have potential as proton exchange membranes. 相似文献
5.
The crosslinked sulfonated poly (ether ether ketone)/2-acrylamido-2-methyl-1-propanesulfonic acid (SPEEK/AMPS) blend membranres were prepared and evaluated as proton exchange membranes for direct methanol fuel cell (DMFC) applications. The structure and morphology of SPEEK/AMPS membranes were characterized by FTIR and SEM, respectively. The effects of crosslinking and AMPS content on the performance of membranes were studied and discussed in detail. The proton conductivity and methanol diffusion coefficient of SPEEK/AMPS membranes increased gradually with the increase of AMPS content. Most SPEEK/AMPS membranes exhibited higher proton conductivity than Nafion® 117 (0.05 S cm−1 at 25 °C). However, all the membranes possessed much lower methanol diffusion coefficient compared with Nafion® 117 (2.38 × 10−6 cm2 s−1) under the same measuring conditions. Even the methanol diffusion coefficient (8.89 × 10−7 cm2 s−1) of SPEEK/AMPS 30 sample with the highest proton conductivity (0.084 S cm−1 at 25 °C) was only about one third of that of Nafion® 117. The selectivity of all the SPEEK/AMPS membranes was much higher in comparison with Nafion® 117 (2.8 × 104 S s cm−3). In addition, the SPEEK/AMPS membranes possessed relatively good thermal and hydrolytic stability. These results suggested that the SPEEK/AMPS membranes were particularly promising to be used as proton exchange membranes in DMFCs, and the high proton conductivity, low methanol diffusion coefficient and high selectivity were their primary advantages for DMFC applications. 相似文献
6.
Ye Li Min XieXitao Wang Danming ChaoXincai Liu Ce Wang 《International Journal of Hydrogen Energy》2013
In this article, novel branched sulfonated poly(ether ether ketone)s (Br-SPEEK) containing various amounts of 1,3,5-tris(4-fluorobenzoyl)benzene as the branching agent have been successfully prepared. Compared with the traditional linear polymer membranes, the membranes prepared by Br-SPEEK showed improved mechanical strength, excellent dimensional stability and superior oxidative stability with similar proton conductivity. Notably, the Br-SPEEK-10 membrane began to break after 267 min in Fenton's reagent at 80 °C, which was 4 times longer than that of the L-SPEEK. Although the proton conductivity decreased with the addition of the branching agent, satisfying methanol permeability value was observed (down to 6.3 × 10−7 cm2 s−1), which was much lower than Nafion 117 (15.5 × 10−7 cm2 s−1). All the results indicated that the novel branched sulfonated poly(ether ether ketone)s membrane was potential candidate as proton conductive membranes for application in fuel cells. 相似文献
7.
HMS-based sulphonated poly(arylene ether sulphone) (HMSSH) is synthesised using 4,4′-dihydroxy-α-methylstilbene (HMS) monomer to introduce an interesting stilbene core as crosslinkable group. Crosslinked blend membranes are obtained by blending the BPA-based sulphonated poly(arylene ether sulphone) (BPASH) with crosslinkable HMS-based sulphonated poly(arylene ether sulphone) by UV irradiation of the blend membrane. Compared to the native BPASH with crosslinked BPASH/HMSSH blend membranes, the crosslinked blend membranes greatly reduce the water uptake and methanol permeability with only a slight reduction in proton conductivity. The crosslinked blend membrane, which has a 6% HMSSH content, has a water uptake of 59%, methanol permeability of 0.75 × 10−6 cm2 s−1, and proton conductivity of 0.08 S cm−1. A membrane-electrode assembly is used to investigate single-cell performance and durability test for DMFC applications. Both the power density and open circuit voltage are higher than those of Nafion® 117. A maximum power density of 32 mW cm−2 at 0.2 V is obtained at 80 °C, which is higher than that of Nafion® 117 (25 mW cm−2). 相似文献
8.
Xinbing Chen Pei ChenZhongwei An Kangcheng ChenKenichi Okamoto 《Journal of power sources》2011,196(4):1694-1703
A series of crosslinkable sulfonated poly(arylene ether ketone)s (SPAEKs) were synthesized by copolymerization of 4,4′-biphenol with 2,6-difluorobenzil and 5,5′-carbonyl-bis(2-fluorobenzene-sulfonate). A facile crosslinking method was successfully developed, based on the cyclocondensation reaction of benzil moieties in polymer chain with 3,3′-diaminobenzidine to form quinoxaline groups acting as covalent and acid-base ionic crosslinking. The uncrosslinked and crosslinked SPAEK membranes showed high mechanical properties and the isotropic membrane swelling, while the later became insoluble in tested polar aprotic solvents. The crosslinking significantly improved the membrane performance, i.e., the crosslinked membranes had the lower membrane dimensional change, lower methanol permeability and higher oxidative stability than the corresponding precursor membranes, with keeping the reasonably high proton conductivity. The crosslinked membrane (C-B4) with an ion exchange capacity of 2.02 mequiv. g−1 showed a reasonably high proton conductivity of 111 mS cm−1 with a low water uptake of 42 wt% at 80 °C. C-B4 exhibited a low methanol permeability of 0.55 × 10−6 cm2 s−1 for 32 wt% methanol solution at 25 °C. The crosslinked SPAEK membranes have potential for PEFC and DMFC applications. 相似文献
9.
Liyuan Zhang Gang Zhang Chengji Zhao Zhongguo Liu Hao Jiang Shuai Xu Mingyu Li Dan Xu Hui Na 《International Journal of Hydrogen Energy》2013
A novel side-chain poly(arylene ether ketone) functionalized with 1,4-butane-sultone (SQNPAEK-x, “x” refers to the number of the attaching sulfobutyl groups in one unit) were synthesized for proton exchange membrane fuel cell. SQNPAEK-x showed high proton conductivity up to 0.317 S cm−1 at 80 °C and excellent dimensional stability due to the remaining hydroxyl groups. Morphological investigations revealed that SQNPAEK-x contained more uniform ionic clusters than the main-chain sulfonated poly(arylene ether ketone), which increased the proton conductivity. Other properties such as water uptake, mechanical properties were also investigated. It should be noted that SQNPAEK-1.5 possesses the best overall performance with proton conductivity (0.204 S cm−1 at 80 °C) higher that Nafion 117, while the swelling ratio was equivalent (13.2% at 80 °C). All the results indicate that the SQNPAEK-x membranes are promising candidates for proton exchange membrane fuel cells. 相似文献
10.
Ye LiZhiliang Li Xiaofeng LuChengcheng Zhang Zhaojie WangLirong Kong Ce WangXincai Liu 《International Journal of Hydrogen Energy》2011,36(22):14622-14631
Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafluoroisopropylidene diphenyl moiety and poly(amic acid) with oligoaniline in the main chain have been prepared and immersed in H3PO4 to obtain acid-doped composite films. As expected, the water uptake values and methanol permeability of the composite membranes decrease with the increase of the weight fraction of PAA in the membrane matrix. Notably, the SPEEK-6F/PAA-15 shows a water uptake of 13.2% and a methanol permeability of 0.9 × 10−7 cm2 s−1, which are much lower than those of the Nafion (28.6% and 15.5 × 10−7 cm2 s−1, respectively). Although the proton conductivities decrease after the addition of PAA, higher selectivity values are obtained with the composite membranes. Therefore, the SPEEK-6F/PAA blend membranes, with the improved proton conductivity, methanol resistance and good thermal stability, can be used as a good alternative for proton conductive membranes with potential application in proton exchange membrane fuel cells (PEMFCs). 相似文献
11.
Haidan Lin 《Journal of power sources》2010,195(11):3380-998
In this study, a new type of cross-linked composite membrane is prepared and considered for its potential applications in direct methanol fuel cell. Nafion and sulfonated poly(arylene ether ketone) bearing carboxylic acid groups (SPAEK-C) are blended and subsequently cross-linked by a Friedel-Craft reaction using the carboxylic acid groups in the SPAEK-C to achieve lower methanol permeability. The perfluoroalkyl sulfonic acid groups of Nafion act as a benign solid catalyst, which assist the cross-linking of SPAEK-C. The physical and chemical characterizations of the cross-linked composite membranes are performed by varying the contents of SPAEK-C. The c-Nafion-15% membrane exhibits appropriate water uptake (10.49-25.22%), low methanol permeability (2.57 × 10−7 cm2 s−1), and high proton conductivity (0.179 S cm−1 at 80 °C). DSC and FTIR analyze suggest the cross-linking reaction. These results show that the self-cross-linking of SPAEK-C in the Nafion membrane can effectively reduce methanol permeability while maintaining high proton conductivity. 相似文献
12.
In polymer electrolyte fuel cell operation, a decrease in the proton conductivity of the membrane at reduced humidity is a main cause for poor cell performance at high temperature. To alleviate the dehydration of the membrane at high temperature, sulfonated mesoporous benzene-silica (sMBS) particles are embedded in sulfonated poly(ether ether ketone) (sPEEK) membranes. As the sMBS itself is highly sulfonated on both organic and inorganic moieties, the proton conductivity of composite membranes is much higher than that of the pristine sPEEK membrane, and it reaches that of Nafion 117 at a high relative humidity (RH) of 90%. The dehydration rate of the membrane is reduced significantly by the capillary condensation effect of sMBS particles with the nanometer-scale 2-D hexagonal cylindrical pores, and the proton conductivity of the composite membranes, 0.234 × 10−1 S cm−1, is much higher than that of pristine sPEEK membrane, 0.59 × 10−3 S cm−1, at a relatively low humidity of 40% RH. This maintenance of high conductivity at low humidity is attributed to the high water-holding capacity of the sMBS proton conductors. The sMBS-embedded sPEEK composite membranes show a much lower methanol permeability of 2–5 × 10−7 cm2 s−1 compared to that of Nafion 117, which is 1.6 × 10−6 cm2 s−1 at room temperature. 相似文献
13.
To prepare a cross-linked proton exchange membrane with low methanol permeability and high proton conductivity, poly (vinyl alcohol) is first blended with sulfonated poly (arylene ether ketone) bearing carboxylic acid groups (SPAEK-C) and then heated to induce a cross-linking reaction between the carboxyl groups in SPAEK-C and the hydroxyl groups in PVA. Fourier transform infrared spectroscopy is used to characterize and confirm the structure of SPAEK-C and the cross-linked membranes. The proton conductivity of the cross-linked membrane with 15% PVA in weight reaches up to 0.18 S cm−1 at 80 °C (100% relative humidity), which is higher than that of Nafion membrane, while the methanol permeability is nearly five times lower than Nafion. The ion-exchange capacity, water uptake and thermal stability are investigated to confirm their applicability in fuel cells. 相似文献
14.
Jing ZhuGang Zhang Ke ShaoChengji Zhao Hongtao LiYang Zhang Miaomiao HanHaidan Lin Mu LiHui Na 《Journal of power sources》2011,196(14):5803-5810
A series of novel hybrid membranes based on sulfonated poly(arylene ether ketone)s (SNPAEKs), polysiloxane (KH-560) and sulfonated curing agent (BDSA) has been prepared by sol-gel and cross-linking reaction for direct methanol fuel cells (DMFCs). All the hybrid membranes (SKB-xx) show high thermal properties and improved oxidative stability compared with the pristine SNPAEK membrane. The sulfonated cross-linked polysiloxanes networks in the hybrid membranes enhance the mechanical properties and reduce the swelling ratio. The swelling ratio of SKB-20 is 22%, which is much lower than that of the pristine SNPAEK (37%) at 80 °C. Meanwhile, SKB-xx membranes with greatly reduced methanol permeabilities show comparative proton conductivities to pristine SNPAEK membranes. Notably, the proton conductivities of SKB-5 and SKB-10 reach to 0.192 S cm−1 and 0.179 S cm−1 at 80 °C, respectively, which are even higher than the 0.175 S cm−1 of SNPAEK. 相似文献
15.
Ki Tae ParkSang Gon Kim Jeong Hwan ChunDong Hyun Jo Byung-Hee ChunWoo In Jang Gyung Bo KangSung Hyun Kim Ki Bong Lee 《International Journal of Hydrogen Energy》2011,36(17):10891-10900
The organic-inorganic composite membranes are prepared by inserting poly(styrene sulfonate)-grafted silica particles into a polymer matrix of sulfonated poly(arylene ether sulfone) copolymer. The first step consisted in using atom transfer radical polymerization method to prepare surface-modified silica particles grafted with sodium 4-styrenesulfonate, referred to as PSS-g-SiO2. Ion exchange capacities up to 2.4 meq/g are obtained for these modified silica particles. In a second step, a sulfonated poly(arylene ether sulfone) copolymer is synthesized via nucleophilic step polymerization of sulfonated 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl sulfone and phenolphthalin monomers in the presence of potassium carbonate. The copolymer is blended with various amounts of silica particles to form organic-inorganic composite membranes. Esterification reaction is carried out between silica particles and the sulfonated polymer chains by thermal treatment in the presence of sodium hypophosphite, which catalyzed the esterification reaction. The water uptake, proton conductivity, and thermal decomposition temperature of the membranes are measured. All composite membranes show better water uptake and proton conductivity than the unmodified membrane. Moreover, the membranes are tested in a commercial single cell at 80 °C and 120 °C in humidified H2/air under different relative humidity conditions. The composite membrane containing 10%(w/w) of PSS-g-SiO2 particles, which have ester bonds between polymer chains and silica particles, showed the best performance of 690 mA cm−2 at 0.6 V, 120 °C and 30 %RH, even higher than the commercial Nafion® 112 membrane. 相似文献
16.
Sulfonated poly(arylene ether ketone) bearing carboxyl groups (SPAEK-C) membranes were first modified by alternating deposition of oppositely charged polyaniline (PANI) and phosphotungstic acid (PWA) via the layer-by-layer method in order to prevent the crossover of methanol in a direct methanol fuel cell. The methanol permeability of SPAEK-C–(PANI/PWA)5 is 2 orders of magnitude less than those of Nafion 117 and pristine SPAEK-C. Furthermore, the modified membrane shows a proton conductivity of 0.093 Scm−1 at 25 °C and 0.24 Scm−1 at 80 °C, which are superior to those of Nafion 117 and pristine SPAEK-C. Fourier transform infrared spectroscopy confirms that PANI and PWA are assembled in the multilayers. The SEM images show the presence of thin PANI/PWA layers coated on the SPAEK-C membrane. Thermal stability, water uptake, water swelling, proton and electron conductivity at different temperature of the SPAEK-C and SPAEK-C-(PANI/PWA)n membranes are also investigated. 相似文献
17.
A novel series of sulfonated poly(arylene ether sulfone)s (SPAESs) containing fluorophenyl pendant groups are successfully developed and their membranes are evaluated in low-temperature proton exchange membrane fuel cells. The SPAESs are synthesized from 4,4′-dichlorodiphenylsulfone (DCDPS), 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone (SDCDPS), and (4-fluorophenyl)hydroquinone by nucleophilic aromatic substitution polycondensation. The structure and properties of SPAESs membranes are characterized using 1H-NMR, EA, FT-IR, TG, and DSC, along with the proton conductivity, water uptake, ion exchange capacity and chemical stability. A maximum proton conductivity of 0.35 S cm−1 at 90 °C is achieved for SPAES membrane with 50% SDCDPS. These SPAES membranes display high dimensional stability and oxidative durability, due to the introduction of fluorophenyl pendant groups on the polymer backbone. The fuel cell performances of the MEAs with SPAES reaches an initial power density of 120.6 mW cm−2 at 30 °C, and greatly increases to 224.3 mW cm−2 at 80 °C using H2 and O2 gases. 相似文献
18.
Haidan Lin 《Journal of power sources》2010,195(3):762-196
To prepare a cross-linked hybrid proton exchange membrane with high mechanical and oxidative stability, a silane monomer, namely 3-glycidoxypropyltrimethoxysilane (KH-560), is first grafted to sulfonated poly(arylene ether ether ketone)s bearing carboxyl groups (SPAEK-C) and hydrolysis-condensation is then performed on the grafted membranes to make them cross-link. 1H NMR measurements and Fourier transform infrared spectroscopy are used to characterize and confirm the structures of SPAEK-Cs and hybrid polymer electrolyte membranes, respectively. The Si-O-Si cross-linking structure enhances the stability of the PEM greatly. The proton conductivities of the hybrid membranes with 5% KH-560 in weight reach 0.155 S cm−1 at 80 °C which is comparable to that of Nafion® membranes. The ion-exchange capacity, water uptake and swelling, methanol permeability, mechanical properties are investigated to confirm their applicability in fuel cells. 相似文献
19.
Hongtao Li Jing Wu Qiong Jia Liyuan Zhang Miaomiao Han Ke Shao Hui Na 《Journal of power sources》2010,195(24):8061-8066
Sulfonated poly(ether ether ketone) containing hydroxyl groups (SPEEK-OH) has been prepared for use as a proton exchange membrane (PEM) by reducing the carbonyl groups on the main chain of the polymers. With the goal of reducing water uptake and methanol permeability, a facile thermal-cross-linking process is used to obtain the cross-linked membranes. The properties of the cross-linked membranes with different cross-linked density are measured and compared with the pristine membrane. Notably, SPEEK-4 with the highest cross-linked density shows a water uptake of 39% and a methanol permeability of 2.52 × 10−7 cm2 s−1, which are much lower than those of the pristine membrane (63.2% and 5.37 × 10−7 cm2 s−1, respectively). These results indicate that this simple approach is very effective to prepare cross-linked proton exchange membranes for reducing water uptake and methanol permeability. 相似文献
20.
《International Journal of Hydrogen Energy》2022,47(11):7443-7457
In this study, the side-chain type hybrid proton exchange membranes which based on metal-organic frameworks (MOFs) and organic matrix of sulfonated poly (arylene ether ketone sulfone) containing both long and short sulfonic acid side chains (S-C-SPAEKS) were prepared. MOF-801 was used as a template and then imidazole was encapsulated into MOF-801 as additional proton carriers. In imidazole -MOF-801, imidazole was used as a functional group to coordinate with the zirconium metal site of the functional group. Imidazole-MOF-801 and hybrid membranes were characterized by XRD, 1H NMR and FT-IR. These hybrid membranes exhibited excellent proton conductivities and good thermal stabilities. Compared to pure S-C-SPAEKS (0.0487 S cm?1 at 30 °C, 0.0809 S cm?1 at 80 °C), S-C-SPAEKS/0.5% Im-MOF-801 showed a great improvement (0.1205 S cm?1 at 30 °C, 0.1992 S cm?1 at 80 °C), which was about 2.5 times higher than that of pure S-C-SPAEKS and 2 times higher than that of commercial Nafion117 (0.1003 S cm?1 at 80 °C). The results indicated that imidazole functionalized MOFs and uneven side chain structure synergistically made an important contribution to proton transport. This series of hybrid membranes have the potential to be used as alternative proton exchange membranes. 相似文献