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1.
Nanoheterostructured material composed of sepiolite clay mineral in which is assembled a MgAl layered double hydroxide (LDH) was used in the preparation of Nafion composite electrolyte membranes and their behavior compared to those of membranes filled with the LDH alone. Both, the neat MgAl LDH and the MgAl LDH-sepiolite hybrid materials were obtained via the co-precipitation method. Sepiolite fibers provide a large external surface area for bonding MgAl LDH particles while maintaining high microporosity and water molecules. The nanocomposite membranes were prepared incorporating different amount of LDH or LDH-sepiolite hybrid. Composite membranes present better water retention, good thermal properties and high proton conductivities at high temperatures than the pure Nafion membrane. The proton conductivity at 100 °C and 100% RH reaches a value of 0.13 S/cm for the LDH-sepiolite Nafion membrane whereas is only 0.010 S/cm in the case of the Nafion membrane. Fuel cell tests using Nafion membranes containing LDH or LDH-sepiolite hybrid as composite electrolytes show a good result for the operation of the PEMFC at 80 °C, 100 °C and 110 °C, with a clear favoring effect of the LDH-sepiolite filler for operation at the highest temperatures.  相似文献   

2.
Composite membranes composed of zirconium phosphate (ZrP) and imidazolium-based ionic liquids (IL), supported on polytetrafluoroethylene (PTFE) were prepared and evaluated for their application in proton exchange membrane fuel cells (PEM) operating at 200 °C. The experimental results reported here demonstrate that the synthesized membrane has a high proton conductivity of 0.07 S cm?1, i.e, 70% of that reported for Nafion. Furthermore, the composite membranes possess a very high proton conductivity of 0.06 S cm?1 when processed at 200 °C under completely anhydrous conditions. Scanning electron microscopy (SEM) images indicate the formation of very small particles, with diameters in the range of 100–300 nm, within the confined pores of PTFE. Thermogravimetric analysis (TGA) reveals a maximum of 20% weight loss up to 500 °C for the synthesized membrane. The increase in proton conductivity is attributed to the creation of multiple proton conducting paths within the membrane matrix. The IL component is acting as a proton bridge. Therefore, these membranes have potential for use in PEM fuel cells operating at temperatures around 200 °C.  相似文献   

3.
A commercial perfluorinated sulfonic acid (PFSA) membrane, Nafion, shows outstanding conductivity under conditions of a fully humidified surrounding. Nevertheless, the use of Nafion membranes that operate only at low temperature (<100 °C) can lead to some disadvantages in PEMFC systems, such as a low impurity tolerance and slow kinetics. To overcome the above problems, this study introduces a highly durable composite membrane with an inorganic filler for a high-temperature proton exchange membrane fuel cell (HT-PEMFC) applications under anhydrous conditions. In this work, polybenzimidazole (PBI) is used as a polymer electrolyte membrane with the addition of a sulfonated graphene oxide (SGO) inorganic filler. The amount of SGO filler was varied (0.5–6 wt.%) to study its influence on proton conductivity at elevated temperature, mechanical stability as well as phosphoric acid doping level. In particular, PBI-SGO composite membranes exhibited higher the level of acid dopant and proton conductivities than those of the pure PBI membranes. The PBI-SGO 2 wt.% composite membrane displayed the highest proton conductivity, with a value of 9.142 mS cm−1 at 25 °C, and it increased to 29.30 mS cm−1 at 150 °C. The PBI-SGO 2 wt.% also displayed the maximum values in the acid doping level (11.63 mol of PA/PBI repeat unit) and mechanical stability (48.86 MPa) analyses. In the HT-PEMFC test, compared with a pristine PBI membrane, the maximum power density was increased by 40% with the use of a PBI composite membrane with 2 wt.% SGO. These results show that the PBI-SGO membrane has a great potential to be applied as an alternative membrane in HT-PEMFC applications, offering the possibility of improving impurity tolerance and kinetic reactions.  相似文献   

4.
《Journal of power sources》2002,109(2):356-364
Various perfluorosulfonic acid membranes (PFSAs) were studied as pure and silicon oxide composite membranes for operation in hydrogen/oxygen proton-exchange membrane fuel cells (PEMFCs) from 80 to 140 °C. The composite membranes were prepared either by impregnation of pre-formed PFSAs via sol–gel processing of a polymeric silicon oxide, recasting a film using solubilized PFSAs and a silicon oxide polymer/gel. All composite membranes had a silicon oxide content of less than or equal to 10% by weight. Decreasing the equivalent weight and thickness of the PFSAs, in addition to the incorporation of silicon oxide helped improve water management in a PEMFC at elevated temperatures. Fourier transform-infrared spectroscopy–attenuated total reflectance (FT-IR–ATR), and scanning electron microscopy (SEM) experiments indicated an evenly distributed siloxane polymer in all of the composite membranes. At a potential of 0.4 V the Aciplex 1004/silicon oxide composite membrane in a humidified H2/O2 PEMFC at 130 °C and a pressure of 3 atm delivered six times higher current density than unmodified Nafion 115 under the same conditions, and 1.73 times the current density when unmodified Nafion 115 was operated with humidified gases at 80 °C and 1 atm of pressure. Furthermore, the PEMFC performances with the PFSA/silicon oxide composite membranes were physically more robust than the control membranes (unmodified PFSAs), which degraded after high operation temperature and thermal cycling.  相似文献   

5.
The short-side-chain (SSC) perfluorosulfonic acid (PFSA) membranes are important candidates as membrane electrolytes applied for high temperature or low relative humidity (RH) proton exchange membrane fuel cells. In this paper, the fuel cell performance, proton conductivity, proton mobility, and water vapor absorption of SSC PFSA electrolytes and the reinforced SSC PFSA/PTFE composite membrane are investigated with respect to temperature. The pristine SSC PFSA membrane and reinforced SSC composite membrane show better fuel cell performance and proton conductivity, especially at high temperature and low relative humidity conditions, compared to the long-side-chain (LSC) Nafion membrane. Under the same condition, the proton mobility of SSC PFSA membranes is lower than that of the LSC PFSA membrane. The water vapor uptake values for Nafion 211 membrane, pristine SSC PFSA membrane and SSC PFSA/PTFE composite membrane are 9.62, 11.13, and 11.53 respectively at 40 °C and they increase to 9.89, 12.55 and 13.09 respectively at 120 °C. The high water content of SSC PFSA membrane makes it maintain high performance even at elevated temperatures.  相似文献   

6.
Proton exchange membranes remain a crucial material and a key challenge to fuel cell science and technology. In this work, new Nafion membranes are prepared by a casting method using aryl- or azaheteroaromatic bisphosphonate compounds as dopants. The incorporation of the dopant, considered at 1 wt% loading after previous selection, produces enhanced proton conductivity properties in the new membranes, at different temperature and relative humidity conditions, in comparison with values obtained with commercial Nafion. Water uptake and ionic exchange capacity (IEC) are also assessed due to their associated impact on transport properties, resulting in superior values than Nafion when tested in the same experimental conditions. These improvements by doped membranes prompted the evaluation of their potential application in fuel cells, at different temperatures. The new membranes, in membrane-electrode assemblies (MEAs), show an increased fuel cell maximum power output with temperature until 60 °C or 70 °C, followed by a decrease above these temperatures, a Nafion-like behaviour when measured in the same conditions. The membrane doped with [1,4-phenylenebis(hydroxymethanetriyl)]tetrakis(phosphonic acid) (BP2) presents better results than Nafion N-115 membrane at all studied temperatures, with a maximum power output performance of ~383 mW cm?2 at 70 °C. Open circuit potentials of the fuel cell were always higher than values obtained for Nafion MEAs in all studied conditions, indicating the possibility of advantageous restrain to gas crossover in the new doped membranes.  相似文献   

7.
Sulfonated covalent organic nanosheets (SCONs) with a functional group (−SO3H) are effective at reducing ion channels length and facilitating proton diffusion, indicating the potential advantage of SCONs in application for proton exchange membranes (PEMs). In this study, Nafion-SCONs composite membranes were prepared by introducing SCONs into a Nafion membrane. The incorporation of SCONs not only improved proton conductivity, but also suppressed methanol permeability. This was due to the even distribution of ion channels, formed by strong electrostatic interaction between the well dispersed SCONs and Nafion polymer molecules. Notably, Nafion-SCONs-0.6 was the best choice of composite membranes. It exhibited enhanced performance, such as high conductivity and low methanol permeability. The direct methanol fuel cell (DMFC) with Nafion-SCONs-0.6 membrane also showed higher power density (118.2 mW cm−2), which was 44% higher than the cell comprised of Nafion membrane (81.9 mW cm−2) in 2 M methanol at 60 °C. These results enabled us to work on building composite membranes with enhanced properties, made from nanomaterials and polymer molecules.  相似文献   

8.
The proton exchange membrane is one of the critical parts of a direct methanol fuel cell. High proton conductivity and low methanol permeability are required. To enhance the performance of a direct methanol fuel cell, graphene oxide was incorporated to Nafion-mordenite composite membranes to enhance the compatibility and to decrease methanol permeability. It was found that the membrane with silane grafted on graphene oxide-treated mordenite with a graphene oxide content of 0.05% presented the highest proton conductivity (0.0560 S·cm−1, 0.0738 S·cm−1 and 0.08645 S·cm−1 at 30, 50, and 70 °C, respectively). This was about 1.6-fold of the recast Nafion and commercial Nafion 117 and was about 1.5-fold of that without graphene oxide incorporation. Finally, the operating condition was optimized using response surface methodology and the maximum power density was investigated. Power density of about 4-fold higher than that of Nafion 117 was obtained in this work at 1.84 M and 72 °C with a %Error between the model prediction and the fuel cell experiment of 0.082%.  相似文献   

9.
In this work, we developed a novel composite membrane by anchoring perfluorosulfonic acid into the hydrophilic poly(lactic-co-glycolic acid) (PLGA) nanofibrous network which was synthesized by electrospinning method. It was clear that the PLGA/Nafion composite membranes possessed high Nafion loading, excellent dimensional stability and proton transport capacity. When the humidity of the membrane changed from soaking in water to 25 RH% at 90 °C, the PLGA fiber network effectively controlled the swelling of Nafion resin and reduced the humidity-generated shrinkage stress from 2.2 MPa (Nafion211 membranes) to 0.5 MPa (PLGA/Nafion composite membranes). The proportion of humidity-induced stress to the yield strength was also reduced to 4.4%, in comparison to 21.2% of that of Nafion211 membrane. The area proton conductivity of the PLGA/Nafion composite membrane achieved 48.2 S cm−2, compared with 36.0 S cm−2 of Nafion211 membranes in the same condition. The excellent proton transport capacity greatly improved the performance of fuel cell assembled with PLGA/Nafion composite membranes and effectively reduced the dynamic response time from 22 s (Nafion211 membranes) to 7 s (PLGA/Nafion composite membranes).  相似文献   

10.
《Journal of power sources》2006,160(1):139-147
Sulfonated poly(etheretherketone) with a cardo group (SPEEK-WC) exhibiting a wide range of degree of sulfonation (DS) was used to prepare polymeric membranes and composite membranes obtained by incorporation of an amorphous zirconium phosphate sulfophenylenphosphonate (Zr(HPO4)(O3PC6H4SO3H), hereafter Zr(SPP)) in a SPEEK-WC matrix. The nominal composition of the composite membranes was fixed at 20 wt% of Zr(SPP). Both types of membrane were characterized for their proton conductivity, methanol permeability, water and/or methanol uptake, morphology by SEM and mechanical properties. For comparison, a commercial Nafion 117 membrane was characterized under the same operative conditions. The composite membranes exhibited a reduced water uptake in comparison with the polymeric membranes especially at high DS values and temperature higher than 50 °C. As a result, the water uptake into composite membranes remained about constant in the range 20–70 °C. The methanol permeability (P) of both polymeric and composite membranes was always lower than that of a commercial Nafion 117 membrane. At 22 °C and 100% relative humidity (RH), the proton conductivities (σ) of the polymeric membranes increased from 6 × 10−4 to 1 × 10−2 S cm−1 with the increase of DS from 0.1 to 1.04. The higher conductivity value was comparable with that of Nafion 117 membrane (3 × 10−2 S cm−1) measured under the same operative conditions. The conductivities of the composite membranes are close to that of the corresponding polymeric membranes, but they are affected to a lesser extent by the polymer DS. The maximum value of the σ/P ratio (about 7 × 104 at 25 °C) was found for the composite membrane with DS = 0.2 and was 2.5 times higher than the corresponding value of the Nafion membrane.  相似文献   

11.
Long-term chemical stability of proton exchange membranes in polymer electrolyte fuel cells (PEFCs) is an important issue for widespread commercialization. Here, we report on the chemical stability of a membrane-electrode assembly with a 7 μm thick pore-filling membrane (porous substrate filled with high ion exchange capacity perfluorosulfonic acid (PFSA) polymer) using an open-circuit voltage hold test. The very thin pore-filling membrane shows comparable chemical durability to Nafion 211. Interestingly, the pore-filling membrane shows a different degradation behavior from Nafion 211 due to the use of chemically and mechanically stable porous substrate, with no thickness change and little amounts of fluorine leakages are observed in the pore-filling membrane compared to membrane thinning and large amounts of fluorine leakage in Nafion 211. The thin pore-filling membrane shows promise for application in PEFCs, as it balances high fuel cell performance at high temperature and low relative humidity with high chemical durability.  相似文献   

12.
With PWA as proton transfer and silica as water retainer, stable phosphotungstic acid/silica/Nafion (PWA/Si–N) composite membrane is non-destructively fabricated and exhibits excellent stability and high temperature proton conductivity. Compared with pristine Nafion, high temperature proton conductivity is significantly enhanced due to the collaboration between –SO3H ionic clusters and the in-situ filled silica embedded PWA nanoparticles. PWA is stabilized in the ionic clusters via in-situ catalyzing the hydrolysis silica precursor targeted filled into the –SO3H ionic clusters. Stable proton conductivity of the PWA/Si–N membrane at 110 °C and 60% RH is high to 0.058 S/cm, which is 2.4 folds of that of Nafion. At the same time, the composite membrane still maintains good mechanical and thermal stability. As a result, high temperature fuel cell performance of the composite membrane is improved by 41% compared with the pristine Nafion membrane. The in-situ coating method proved to be an effective method to solve the stability of PWA in Nafion membrane, especially the inorganic oxide with good hygroscopicity as the modifier.  相似文献   

13.
Dimensional change and humidity-induced stress of the proton exchange membrane were demonstrated to be main reasons for membrane physical failure during the long-term fuel cell operation. In this work, UV laser ablation was proposed to prepare physically stable polyimide supports to reduce the dimensional swelling and humidity-induced stress of the proton exchange membrane under variable humidities. Long-range ordered straight holes with definable open pattern and diameter of 50–200 μm were formed through the polyimide support. Composite proton exchange membrane prepared from the straight-hole polyimide support presented desirable performance and high durability in fuel cells. When Nafion fraction in the composite membrane increased to 48.67%, the proton conductivities of the composite membranes were equal to or greater than that of the conventional Nafion membrane with activation energies lower than that of the Nafion 211 membrane. The dimensions of the composite membranes are very stable in both low and elevated temperature conditions. The proportion of humidity-induced stress to the yield strength for the composite membrane is 0.20%–0.21%, much lower than that of the conventional Nafion membrane (24.77%). As a result, the composite proton exchange membrane prepared from the straight-hole polyimide presented high durability in the fuel cell operation. In the open circuit voltage accelerated test under in situ accelerating RH cyclic test, the irreversible OCV reduction rate of the composite membranes was 2.41–2.72 × 10−5 V/cycle, 37.1%–41.8% lower than that of the conventional Nafion 211 membrane.  相似文献   

14.
Synthesis and characterization of Nafion/TiO2 membranes for proton exchange membrane fuel cell (PEMFC) operating at high temperatures were investigated in this study. Nafion/TiO2 nanocomposite membranes have been prepared by in-situ sol–gel and casting methods. In the sol–gel method, preformed Nafion membranes were soaked in tetrabutylortotitanate (TBT) and methanol solution. In order to compare synthesis methods, a Nafion/TiO2 composite membrane was fabricated with 3 wt.% of TiO2 particles by the solution casting method. The structures of membranes were investigated by Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and Energy Dispersive X-Ray Analysis (EDXA). Also, water uptake and proton conductivity of modified membranes were measured. Furthermore, the membranes were tested in a real PEMFC. X-Ray spectra of the composite membranes indicate the presence of TiO2 in the modified membranes. In case of the same doping level, sol–gel method produces more uniform distribution of Ti particles in Nafion/TiO2 composite membrane than the ones produced by casting method. Water uptake of Nafion/TiO2 membrane with 3 wt.% of doping level was found to be 51% higher than that of the pure Nafion membrane. EIS measurements showed that the conductivity of modified membranes decreases with increasing the amount of doped TiO2. Finally, the membrane electrode assembly (MEA) prepared from Nafion/Titania nanocomposite membrane shows the highest PEMFC performance in terms of voltage vs. current density (V–I) at high temperature (110 °C) which is the main goal of this study.  相似文献   

15.
Synthesis and characterization of nanocomposite membranes for proton exchange membrane fuel cell (PEMFC) operating at different temperatures and humidity were investigated in this study. Recast Nafion composite membrane with ZrO2 and TiO2 nanoparticles with 75 nm in mean size diameter, prepared for PEM fuel cells. Nafion/TiO2 composite membranes have been also fabricated by in-situ sol–gel method. However, fine particles of the ZrO2 were synthesized and Nafion/ZrO2 composite membrane were produced by blending a 5% (w/w) Nafion-water dispersion with the inorganic compound. All nanocomposite membranes demonstrated higher water retention in comparison with unmodified membranes. Proton conductivity increased with increasing ZrO2 content while TiO2 additive (with mean size of 25 nm) enhanced water retention. Subsequently, structures of the membranes were investigated by Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) as well as X-Ray Diffraction (XRD). In addition, water uptake and proton conductivity of the modified membranes were also measured. The nanocomposite membrane was tested in a 25 cm2 commercial single cell at the temperature range of 80–110 °C and in humidified H2/O2 under different relative humidity (RH) conditions. The membrane electrode assembly (MEA) prepared from Nafion/TiO2, ZrO2 presented highest PEM fuel cell performance in respect of IV polarization under condition of 110 °C, 0.6 V and 30% RH and 1 atm.  相似文献   

16.
Composite membranes made from Nafion ionomer with nano phosphonic acid-functionalised silica and colloidal silica were prepared and evaluated for proton exchange membrane fuel cells (PEMFCs) operating at elevated temperature and low relative humidity (RH). The phosphonic acid-functionalised silica additive obtained from a sol–gel process was well incorporated into Nafion membrane. The particle size determined using transmission electron microscope (TEM) had a narrow distribution with an average value of approximately 11 nm and a standard deviation of ±4 nm. The phosphonic acid-functionalised silica additive enhanced proton conductivity and water retention by introducing both acidic groups and porous silica. The proton conductivity of the composite membrane with the acid-functionalised silica was 0.026 S cm−1, 24% higher than that of the unmodified Nafion membrane at 85 °C and 50% RH. Compared with the Nafion membrane, the phosphonic acid-functionalised silica (10% loading level) composite membrane exhibited 60 mV higher fuel cell performance at 1 A cm−2, 95 °C and 35% RH, and 80 mV higher at 0.8 A cm−2, 120 °C and 35% RH. The fuel cell performance of composite membrane made with 6% colloidal silica without acidic group was also higher than unmodified Nafion membrane, however, its performance was lower than the acid-functionalised silica additive composite membrane.  相似文献   

17.
The objective of this work is to examine the polybenzimidazole (PBI)/sulfonated graphene oxide (sGO) membranes as alternative materials for high-temperature proton exchange membrane fuel cell (HT-PEMFC). PBI/sGO composite membranes were characterized by TGA, FTIR, SEM analysis, acid doping&acid leaching tests, mechanical analysis, and proton conductivity measurements. The proton conductivity of composite membranes was considerably enhanced by the existence of sGO filler. The enhancement of these properties is related to the increased content of –SO3H groups in the PBI/sGO composite membrane, increasing the channel availability required for the proton transport. The PBI/sGO membranes were tested in a single HT-PEMFC to evaluate high-temperature fuel cell performance. Amongst the PBI/sGO composite membranes, the membrane containing 5 wt. % GO (PBI/sGO-2) showed the highest HT-PEMFC performance. The maximum power density of 364 mW/cm2 was yielded by PBI/sGO-2 membrane when operating the cell at 160 °C under non humidified conditions. In comparison, a maximum power density of 235 mW/cm2 was determined by the PBI membrane under the same operating conditions. To investigate the HT-PEMFC stability, long-term stability tests were performed in comparison with the PBI membrane. After a long-term performance test for 200 h, the HT-PEMFC performance loss was obtained as 9% and 13% for PBI/sGO-2 and PBI membranes, respectively. The improved HT-PEMFC performance of PBI/sGO composite membranes suggests that PBI/sGO composites are feasible candidates for HT-PEMFC applications.  相似文献   

18.
Modified Nafion membranes by self-assembling of palladium composite nanoparticles were successfully synthesized and used for the reduction of methanol crossover in Direct Methanol Fuel Cells (DMFC). The positively charged polydiallyldimethylammonium (PDDA) was used for stabilizing the palladium nanoparticles. Modified and unmodified membranes were tested in a DMFC at 30 °C and 50 °C. The performance of the DMFC using modified membranes with different composite nanoparticles (i.e., Pd/PDAA ratios) and self-assembling times was compared with that using an unmodified membrane. The modified Nafion membranes proved to reduce the methanol crossover in ca. 10% – 35%, depending on the self-assembling time, nanoparticles composition and test temperature. However, a decrease in the performance was observed mainly for the modified membrane with the higher PDDA content due to a decrease in the proton conductivity. On the other hand, the membrane modified with nanoparticles containing less PDDA and tested at 50 °C showed similar performance as the unmodified one. Additionally, the fuel cell efficiencies obtained for all the modified membranes at both temperatures were similar or higher than the unmodified one.  相似文献   

19.
This study examined methanol crossover through PtRu/Nafion composite membranes for the direct methanol fuel cell. For this purpose, 0.03, 0.05 and 0.10 wt% PtRu/Nafion composite membranes were fabricated using a solution impregnation method. The composite membrane was characterized by inductively coupled plasma-mass spectroscopy and thermo-gravimetric analysis. The methanol permeability and proton conductivity of the composite membranes were measured by gas chromatography and impedance spectroscopy, respectively. In addition, the composite membrane performance was evaluated using a single cell test. The proton conductivity of the composite membrane decreased with increasing number of PtRu particles embedded in the pure Nafion membrane, while the level of methanol permeation was retarded. From the results of the single cell test, the maximum performance of the composite membrane was approximately 27% and 31% higher than that of the pure Nafion membrane at an operating temperature of 30 and 45 °C, respectively. The optimum loading of PtRu was determined to be 0.05 wt% PtRu/Nafion composite membrane.The PtRu particles embedded in the Nafion membrane act as a barrier against methanol crossover by the chemical oxidation of methanol on embedded PtRu particles and by reducing the proton conduction pathway.  相似文献   

20.
Proton exchange membranes with a wide application temperature range were fabricated to start high-temperature fuel cells under room temperature. The volume swelling stability, oxidative stability as well as mechanical properties of crosslinked membranes have been improved for covalently crosslinking poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI) with fluorine-terminated sulfonated poly(ether ether ketone) (F-SPEEK) via N-substitution reactions. High proton conductivity was simultaneously realized at both high (80–160 °C) and low (40–80 °C) temperatures by crosslinking and jointly constructing hydrophilic-hydrophobic channels. The crosslinked membranes exhibited the highest proton conductivity of 191 mS cm−1 at 80 °C under 98% relative humidity (RH) and 38 mS cm−1 at 160 °C under anhydrous, respectively. Compared with OPBI membrane, the fuel cell performance of the crosslinked membranes showed higher peak power density at full temperature range (40–160 °C).  相似文献   

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