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1.
A new class of covalently cross-linkable poly(arylene ether ketone)s (cPAEKs) with sulfonic acid groups on both the backbone and pedant positions were synthesized. 3-Amino-1,5-napthalene disulfonic acid salt was chosen as a strong sulfonating agent for the preparation of csPAEK membranes with high sulfonation degree (SD). The major advantage of synthesized membranes is their exceptionally high-proton conductivities but still maintaining low methanol permeability and water uptake. All csPAEK membranes exhibited higher proton conductivity than Nafion®117 over the temperature range of 40–90 °C. For example, among these membranes, csPAEK0 with the lowest SD shows a proton conductivities of 0.071 S cm−1 at 40 °C and 0.118 S cm−1 at 90 °C, which are higher than those of Nafion®117 (0.057 S cm−1 at 40 °C and 0.108 S cm−1 at 90 °C). More interestingly, csPAEK0 appears to have a low water uptake, with values of only 22% at 40 °C and 27% at 90 °C, indicating high dimensional stability in hot water. Moreover, in many cases, csPAEK membranes with 15% cross-linking degree (CD) exhibited low methanol permeability, good thermal stability, and showed very high strain at break. The superior proton conduction, methanol permeation, and water uptake properties of the prepared membranes are of significant interest for both PEMFCs and DMFCs applications.  相似文献   

2.
Fluorous copolymers are synthesized by grafting quaternary ammonium-functionalized 4-vinylbenzyl chloride (QVBC) and N-Isopropyl acrylamide (NIPAAM) from poly(vinylidene fluoride) (PVDF) via atom transfer radical polymerization (ATRP). Ionic PQVBC and thermo-responsive PNIPAAM grafts are characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. Polarity difference between flexible grafts and rigid fluorous backbones allows convenient formation of ionic clusters, which impart resultant membranes excellent hydroxide conductivities in the range of 21–52 mS cm−1 at 20 °C, and up to 98 mS cm−1 at 70 °C. Moreover, amide–amide interactions between thermo-responsive grafts at high temperature can mitigate water swelling of hydrophilic clusters. This study suggests that the fluorous copolymer bearing both ionic and thermo-responsive grafts holds a promising selectivity as novel materials for anion exchange membrane with enhanced hydroxide conductivity and controlled water swelling.  相似文献   

3.
A highly sulfonated poly (ether ether ketone) with pendant amino groups (Am-SPEEK) has been synthesized. The resulting copolymer showed good solubility in common organic solvents. Then the pendant amino groups of the Am-SPEEK were utilized to react with two kinds of cross-linker, epoxy resin and dibromide, to yield various cross-linked membranes. After cross-linking, the membranes could not dissolve in common solvents, just became swollen. In generally, all the cross-linked membranes showed improved mechanical properties and high dimensional stabilities, whereas the uncross-linked membranes highly swollen or even dissolved in water at high temperature. The proton conductivity of the membranes increased with an increase in temperature. At 80 °C, all the cross-linked membranes showed high proton conductivity, in the range of 0.111–0.140 S cm−1. Especially, the TMBP cross-linked membrane showed a proton conductivity of 0.140 S cm−1, which was higher than that of Nafion 117 (0.125 S cm−1). The membranes with high proton conductivity, good oxidative stability, and improved methanol residence have been successfully developed. Furthermore, the influence of different main chain of the cross-linker on the performance of the cross-linked membranes was also investigated.  相似文献   

4.
Proton conductive individual channels through a poly(vinyl di-fluoride) PVDF matrix have been designed using the ion track grafting technique. The styrene molecules were radiografted and further sulfonated leading to sulfonated polystyrene (PSSA) domains within PVDF. The grafting process all along the cylindrical ion tracks creates after functionalisation privileged paths perpendicular to the membrane plane for proton conduction from the anode to the cathode when used in fuel cells. Such ion track grafted PVDF-g-PSSA membranes have low gas permeation properties against H2 and O2. A degree of grafting (Yw) of 140% was chosen to ensure a perfect coverage of PSSA onto PVDF-g-PSSA surface minimizing interfacial ohmic losses with the active layers of the Membrane Electrolyte Assembly (MEA). A three-day fuel cell test has been performed feeding the cell with pure H2 and O2, at the anode and cathode side respectively. Temperature has been progressively increased from 50 to 80 °C. Polarisation curves and Electrochemical Impedance Spectroscopy (EIS) at different current densities were used to evaluate the MEA performance. From these last measurements, it has been possible to determine the resistance of the MEA during the fuel cell tests and, thus the membrane conductivity. The proton conductivities of such membranes estimated during fuel cell tests range from 50 mS cm−1 to 80 mS cm−1 depending on the operating conditions. These values are close to that of perfluorosulfonated membrane such as Nafion® in similar conditions.  相似文献   

5.
One of the major challenges for direct methanol fuel cells is the problem of methanol crossover. With the aim of solving this problem without adverse effects on the membrane conductivity, Nafion/Palladium–silica nanofiber (N/Pd–SiO2) composite membranes with various fiber loadings were prepared by a solution casting method. The silica-supported palladium nanofibers had diameters ranging from 100 nm to 200 nm and were synthesized by a facile electro-spinning method. The thermal properties, ionic exchange capacities, water uptake, proton conductivities, methanol permeabilities, chemical structures, and micro-structural morphologies were determined for the prepared membranes. It was found that the transport properties of the membranes were affected by the fiber loading. All of the composite membranes showed higher water uptake and ion exchange capacities compared to commercial Nafion 117 and proved to be thermally stable for use as proton exchange membranes. The composite membranes with optimum fiber content (3 wt%) showed an improved proton conductivity of 0.1292 S cm−1 and a reduced methanol permeability of 8.36 × 10−7 cm2 s−1. In single cell tests, it was observed that, the maximum power density measured with composite membrane is higher than those of commercial Nafion 117.  相似文献   

6.
End-group crosslinked sulfonated poly(arylene sulfide nitrile) (XESPSN) membranes are prepared to investigate the effect of crosslinking on the properties of sulfonated aromatic polymer membranes at elevated temperatures (>100 °C). The morphological transformation during annealing and crosslinking is confirmed by atomic force microscopy. The XESPSN membranes show outstanding thermal and mechanical properties compared to pristine and non-crosslinked ESPSN and Nafion® up to 200 °C. In addition, the XESPSN membranes exhibit higher proton conductivities (0.011–0.023 S cm−1) than the as-prepared pristine ESPSN (0.004 S cm−1), particularly at elevated temperature (120 °C) and low relative humidity (35%) conditions due to its well-ordered hydrophilic morphology after crosslinking. Therefore, the XESPSN membranes demonstrate significantly improved maximum power densities (415–485 mW cm−2) compared to the ESPSN (281 mW cm−2) and Nafion® (314 mW cm−2) membranes in single cell performance tests conducted at 120 °C and 35% relative humidity. Furthermore, the XESPSN membrane exhibits a much longer duration than the ESPSN membrane during fuel cell operation under a constant current load as a result of its improved mechanical and thermal stabilities.  相似文献   

7.
Organic–inorganic hybrid membranes based on poly(methyl methacrylate) (PMMA)/silica have been synthesized using a sol-gel technique for use in polymer electrolyte fuel cells (PEFCs). The properties of these membranes were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results indicate that these membranes are formed through hydrogen bonds between the carbonyl group of PMMA and the uncondensed alcohol functional groups of the inorganic clusters. The proton conductivity of these membranes is on the order of 10−1 S cm−1, and the 60PMMA–30SiO2–10P2O5 membrane displays the highest proton conductivity of 3.85 × 10−1 S cm−1 at 90 °C and 50% RH. The performance of a fuel cell using these membranes was tested. A maximum power density of 370 mW cm−2 is obtained at 80 °C, and the current density at 0.4 V remains almost unchanged during the 100-h test time under the test conditions. This class of hybrid membranes is an extremely promising material for use in PEFCs.  相似文献   

8.
This work describes the synthesis and evaluation of nanocomposite membranes based on calcium phosphate (CP)/ionic liquids (ILs) for high-temperature proton exchange membrane (PEM) fuel cells. Several composite membranes were synthesized by varying the mass ratios of ILs with respect to the CP and all supported on porous polytetrafluoroethylene (PTFE). The membranes exhibit high proton conductivities. Two ionic liquids were investigated in this study, namely, 1-Hexyl-3- methylimidazolium tricyanomethanide, [HMIM][C4N3], and 1-Ethyl-3-methylimidazolium methanesulfonate, [EMIM][CH3O3S]. At room temperature, the CP/PTFE/[HMIM][C4N3] composite membrane possessed a high proton conductivity of 0.1 S cm−1. When processed at 200 °C, and fully anhydrous conditions, the membrane showed a conductivity of 3.14 × 10−3 S cm−1. Membranes based on CP/PTFE/[EMIM][CH3O3S] on the other hand, had a maximum proton conductivity of 2.06 × 10−3 S cm−1 at room temperature. The proton conductivities reported in this work appear promising for the application in high-temperature PEMFCs operated above the boiling point of water.  相似文献   

9.
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.  相似文献   

10.
(Ba0.5Sr0.5)(Fe1-xAlx)O3-δ (BSFAx, x = 0–0.2) oxides have been synthesized as novel cobalt-free cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs) using a sol-gel method. The BSFAx (x = 0–0.2) materials have been characterized by X-ray diffraction and scanning electron microscopy. The electrical conductivities and electrochemical properties of the prepared samples have also been measured. At 800 °C, the conductivity drops from 15 S cm−1 to 5 S cm−1 when the doping level of aluminum is increased to 20%. The aluminum-doping concentration has important impacts on the electrochemical properties of BSFAx materials. The BSFA0.09 cathode shows a significantly lower polarization resistance (0.26 Ω cm2) and cathodic overpotential value (55 mV at the current density of 0.1 A cm−2) at 800 °C. Furthermore, an anode-supported single cell with BSFA0.09 cathode has been fabricated and operated at a temperature range from 650 to 800 °C with humidified hydrogen (∼3vol% H2O) as the fuel and the static air as the oxidant. A maximum power density of 676 mWcm−2 has been achieved at 800 °C for the single cell. We believe that BSFA0.09 is a promising cathode material for future IT-SOFCs application.  相似文献   

11.
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   

12.
To develop a series of cross-linked anion exchange membranes for application in fuel cells, poly(ethylene-co-tetrafluoroethylene) (ETFE) films was radiation grafted with vinyl benzyl chloride (VBC), followed by quaternization and crosslinking with 1,4-Diazabicyclo[2,2,2]octane (DABCO), alkylation with p-Xylylenedichloride (DCX), and quaternization again with trimethylamine (TMA). These anion exchange membranes were characterized in terms of water uptake, ion-exchange capacity, ionic conductivity as well as thermal stability. The chemical structures of the membranes were examined by FT-IR. The anion conductivity of the resulting alkaline anion exchange membrane is as high as 0.039 S cm−1 at 30 °C in deionized water and the ionic conductivity increases with the increasing of temperature from 20 to 80 °C. The membrane is stable after being treated by 10 M potassium hydroxide solution at 60 °C for 120 h .The fuel cell performance with the final AAEM obtained in a H2/O2 single fuel cell at 40 °C with this AAEM was 48 mW cm−2 at a current density of 69 mA cm−2.  相似文献   

13.
An investigation of several electrode parameters on performance of an alkaline membrane fuel cell is described. The studied parameters were: ionomer content, anode and cathode catalyst layer thickness, electrode aminating agent and membrane thickness.It was found that an optimum ionomer content depended on a balance between the OH ion/water mobility and the oxygen solubility/diffusivity through it and which varied with temperature. Thick catalyst layers were necessary for the anode as thin anode catalyst layers suffered from flooding. 40%Pt/C provided the best thickness (with loading of 0.4 mgPt cm−2) for cathodes operating with air.An aminated low density poly(ethylene-co-vinyl benzyl chloride) (LDPE-VBC) membrane was shown to be a good membrane for an alkaline membrane fuel cell, giving conductivities up to 0.13 S cm−1 at 80 °C. A Membrane Electrode Assembly (MEA) utilizing this membrane with fully hydrated thickness of 57 μm produced good peak power density, at a high potential of 500 mV, of 337 mW cm−2 with air (1 bar gauge) at 60 °C.  相似文献   

14.
A series of imidazolium-functionalized polysulfones were successfully synthesized by chloromethylation-Menshutkin two-step method. PSf-ImOHs show the desired selective solubility: insoluble in alcohols (e.g., methanol and ethanol), and soluble in 50 vol.% aqueous solutions of acetone or tetrahydrofuran, implying their potential applications for both the alcohol-resistant membranes themselves and the ionomer solutions in low-boiling-point water-soluble solvents. PSf-ImOH also possesses very high thermal stability (TOD: 258 °C), higher than quaternary ammonium and quaternary phosphonium functionalized polysulfones (TOD: 120 °C and 186 °C, repsectively). Ion exchange capacity (IEC) of PSf-ImOH membranes ranges from 0.78 to 2.19 mmol g−1 with degree of chloromethylation from 42% to 132% of original chloromethylated polysulfone. As expected, water uptake, swelling ratio, and hydroxide conductivity increase with IEC and temperatures. With 2.19 mmol g−1 of IEC, the PSf-ImOH 132% membrane exhibits the highest hydroxide conductivity (53 mS cm−1 at 20 °C), higher than those of all other reported polysulfone-based HEMs (1.6–45 mS cm−1) and other imidazolium-functionalized HEMs (19.6–38.8 mS cm−1). In addition, PSf-ImOH membranes have low methanol permeability of 0.8–4.7 × 10−7 cm2 s−1, one order of magnitude smaller than that of Nafion212 membrane. All these properties indicate imidazolium-functionalized polysulfone is very promising for potential applications in alkaline membrane direct alcohol fuel cells.  相似文献   

15.
Metal-organic frameworks (MOFs) are considered emerging materials as they further improve the various properties of polymer membranes used in energy applications, ranging from electrochemical storage and purification of hydrogen to proton exchange membrane fuel cells. Herein, we fabricate composite membranes consisting of polybenzimidazole (PBI) polymer as a matrix and MOFs as filler. Synthesis of ZIF-8 and UiO-66 MOFs are conducted through a typical solvothermal method, and composite membranes are fabricated with different MOF compositions (e.g., 2.5, 5.0, 7.5, and 10.0 wt %). We report a significant improvement in proton conductivity compared with the pristine PBI; for example, more than a three-fold increase in conductivity is observed when the PBI-UiO66 (10.0 wt %) and PBI-ZIF8 (10.0 wt %) membranes are tested at 160 °C. Proton conductivities of the composite membranes vary between 0.225 and 0.316 S cm?1 at 140 and 160 °C. For the comparison, pure PBI exhibits 0.060 S cm?1 at 140 °C and 0.083 S cm?1 at 160 °C. However, we also report a decrease in permeability and mechanical stability with the composite membranes.  相似文献   

16.
Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm?1 at 40 °C and 45.5 mS cm?1 at 95 °C, respectively.  相似文献   

17.
Novel proton-conducting polymer electrolyte membranes have been prepared from bacterial cellulose by incorporation of phosphoric acid (H3PO4/BC) and phytic acid (PA/BC). H3PO4 and PA were doped by immersing the BC membranes directly in the aqueous solution of H3PO4 and PA, respectively. Characterizations by FTIR, TG, TS and AC conductivity measurements were carried out on the membrane electrolytes consisting of different H3PO4 or PA doping level. The ionic conductivity showed a sensitive variation with the concentration of the acid in the doping solution through the changes in the contents of acid and water in the membranes. Maximum conductivities up to 0.08 S cm−1 at 20 °C and 0.11 S cm−1 at 80 °C were obtained for BC membranes doped from H3PO4 concentration of 6.0 mol L−1 and, 0.05 S cm−1 at 20 °C and 0.09 S cm −1 at 60 °C were obtained for BC membranes doped from PA concentration of 1.6 mol L−1. These types of proton-conducting membranes share not only the good mechanical properties but also the thermal stability. The temperature dependences of the conductivity follows the Arrhenius relationship at a temperature range from 20 to 80 °C and, the apparent activation energies (Ea) for proton conduction were found to be 4.02 kJ mol−1 for H3PO4/BC membrane and 11.29 kJ mol−1 for PA/BC membrane, respectively. In particular, the membrane electrode assembly fabricated with H3PO4/BC and PA/BC membranes reached the initial power densities of 17.9 mW cm−2 and 23.0 mW cm−2, which are much higher than those reported in literature in a real H2/O2 fuel cell at 25 °C.  相似文献   

18.
A highly durable proton exchange membranes (PEM)s based on covalently supported ionic liquid (IL) bearing sulfonic acid imidazolium groups were successfully fabricated. The membrane preparation involved radiation induced grafting of 1-vinyl imidazole (1-VIm) onto poly(ethylene-co-tetraflouroethene) (ETFE) film, followed by covalent immobilization of 3-sulfopropyl and subsequent treatment with trifluoromethanesulfonic acid. The ionic conductivity of the supported IL membranes was increased with the increase in the concentration of IL and reached a maximum value of 138 mS cm−1 in a fully hydrated state with an ion exchange capacity of 4.82 mmol g−1 that is higher than Nafion with a similar thickness. The membranes displayed excellent chemical and mechanical stability. In addition, the dimensional and thermal stability of supported IL-membranes were significantly higher than commercial Nafion membranes.  相似文献   

19.
Poly(styrene sulfonic acid)/poly(vinyl alcohol) proton-conducting membranes with semi-interpenetrating networks (semi-IPNs) were prepared using a modified two-step crosslinking strategy. We previously employed sulfosuccinic acid (SSA) and glutaraldehyde (GA) as crosslinking agents to form a dense hydrophobic layer at the outer membrane surface. Although the proton conductivity of the resulting membrane increased with the content of SSA, the methanol permeability also increased. In this study it was found that the introduction of a sufonating agent, with a high molecular weight, i.e. poly(styrene sulfonic acid) (PSSA), at a PSSA/poly(vinyl alcohol) (g g−1) ratio greater than 0.72, increased the density of the tangled IPN structures that effectively impede the membrane's permeability to MeOH, while enhancing its proton conductivity. The synthesized semi-IPN membranes exhibited high proton conductivities (up to 5.88 × 10−2 S cm−1 at room temperature, i.e. greater than those of Nafion membranes) and high resistances to MeOH permeation (ca. 1 × 10−7 cm2 S−1, that is approximately one order of magnitude lower than that of Nafion membranes).  相似文献   

20.
Perovskite oxide SrCo0.7Fe0.2Ta0.1O3−δ (SCFT) was synthesized by a solid–state reaction and investigated as a potential cathode material for intermediate-temperature solid oxide fuel cell (IT-SOFC). The single phase SCFT having a cubic perovskite structure was obtained by sintering the sample at 1200 °C for 10 h in air. Introduction of Ta improved the phase stability of SCFT. The SCFT exhibited a good chemical compatibility with the La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) electrolyte at 950 °C for 10 h. The average thermal expansion coefficient was 23.8 × 10−6 K−1 between 30 and 1000 °C in air. The electrical conductivities of the SCFT sample were 71–119 S cm−1 in the 600−800 °C temperature range in air, and the maximum conductivity reached 247 S cm−1 at 325 °C. The polarization resistance of the SCFT cathode on the LSGM electrolyte was 0.159 Ω cm2 at 700 °C. The maximum power density of a single-cell with the SCFT cathode on a 300 μm-thick LSGM electrolyte reached 652.9 mW cm−2 at 800 °C. The SCFT cathode had shown a good electrochemical stability over a period of 20 h short-term testing. These findings indicated that the SCFT could be a suitable alternative cathode material for IT-SOFCs.  相似文献   

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