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1.
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   

2.
Here we report a composite electrolyte membrane of Polybenzimidazole (PBI) with Phosphosilicate nano-network (PPSN) for enhanced proton conductivity, durability and power generation of high temperature polymer electrolyte membrane fuel cell (HT-PEMFC). Solid state proton conductor three dimensional Phosphosilicate nano-network (average particle size <10 nm) is synthesized using easy and low-cost sol gel method followed by ball milling and composited with PBI at different loading employing methane sulfonic acid (MSA) as solvent. The electrolyte membrane is characterized using FESEM, XRD, FTIR, TGA; proton conductivity, ion exchange capacity, water uptake and acid doping level, chemical stability and mechanical yield strength are measured and the membrane is tested for HT-PEMFC application. Property and performance mapping reveals that with 10% PPSN loading, composite (PPSN-PBI-10) membrane offers the maximum enhancement of all properties and power generation of HT-PEMFC, while beyond a critical loading (~22%) properties and performance deteriorate below that of pristine PBI. Using optimum loading of PPSN, compared to pristine PBI, a remarkable rise in water uptake and acid doping level is achieved that facilitates proton conduction; also in spite of the presence of Phosphoric acid in the PPSN filler, the maximum 47.5% enhancement of ultimate strength is attained. The performance of HT-PEMFC using composite PPSN-PBI unveil that almost 2 times (100%) enhancement of peak power generation (~0.73 W cm?2) is achieved using PPSN-PBI-10 at 170 °C operating temperature compared to pristine PBI. This may be attributed to the facilitated proton conduction through the extended tunnelling network offered by PPSN. Incorporation of PPSN improves the durability; over 48 h only 16% decay in voltage is noticed using PPSN-PBI-10 membrane which is remarkably lower than the 31% decay of pristine PBI membrane.  相似文献   

3.
High temperature Proton Exchange Membrane Fuel Cells (HT-PEMFC) have attracted the attention of researchers in recent years due to their advantages such as working with reformed gases, easy heat management and compatibility with micro-cogeneration systems. In this study, it is aimed to designed, manufactured and tested of the HT-PEMFC stack based on Polybenzimidazole/Graphene Oxide (PBI/GO) composite membranes. The micro-cogeneration application of the PBI/GO composite membrane based stack was investigated using a reformat gas mixture containing Hydrogen/Carbon Dioxide/Carbon Monoxide (H2/CO2/CO). The prepared HT-PEMFC stack comprises 12 cells with 150 cm2 active cell area. Thermo-oil based liquid cooling was used in the HT-PEMFC stack and cooling plates were used to prevent coolant leakage between the cells. As a result of HT-PEMFC performance studies, maximum 546 W and 468 W power were obtained from PBI/GO and PBI membranes based HT-PEMFC stacks respectively. The results demonstrate that introducing GO into the PBI membranes enhances the performance of HT-PEMFC technology and demonstrated the potential of the HT-PEMFC stack for use in micro-cogeneration applications. It is also underlined that the developed PBI/GO composite membranes have the potential as an alternative to commercially available PBI membranes in the future.  相似文献   

4.
Composite membranes used for proton exchange membrane fuel cells comprising of polybenzimidazole (PBI) and carbon nanotubes with certain functional groups were studied, because they could enhance both the mechanical property and fuel cell performance at the same time. In this study, sodium poly(4-styrene sulfonate) functionalized multiwalled carbon nanotubes (MWNT-poly(NaSS))/PBI and imidazole functionalized multiwalled carbon nanotubes (MWNT-imidazole)/PBI composite membranes were prepared. The functionalization of carbon nanotubes involving non-covalent modification and covalent modification were confirmed by FITR, XPS, Raman spectroscopy, and TGA. Compared to unmodified MWNTs and MWNT-poly(NaSS), MWNT-imidazole provided more significant mechanical reinforcement due to its better compatibility with PBI. For MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes at their saturated doping levels, the proton conductivities were up to 5.1 × 10−2 and 4.3 × 10−2 S/cm at 160 °C under anhydrous condition respectively, which were slightly higher than pristine PBI (2.8 × 10−2 S/cm). Also, MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes showed relatively improved fuel cell performance at 170 °C compared to pristine PBI.  相似文献   

5.
In this study, composite cation exchange membranes (CEM) were developed. With the experience from widely studied proton exchange membrane fuel cells (PEMFC), sulfonated polyether ether ketone (SPEEK) was prepared to be a more effective and cheaper ionomer alternative to the industry standard Nafion ®. SPEEK polymer membrane can reach sufficient ionic conductivities but have some mechanical and chemical stability problems (at a high degree of sulfonations (DS)). Therefore, in order to optimize the membrane, composite mixing with a well-known organic/inorganic clays called Cloisite® 15A, Cloisite ® 30B and MMT were used. Test cells for both single-cell and conductivity were designed and constructed. The ionic conductivity cell was different than the ones used in most studies, measuring conductivity in-plane with 4 probes using EIS. The membranes were characterized for their proton conductivity with electrochemical impedance spectroscopy (EIS), for DS with H NMR, water uptake, and fuel cell performance tests. First results showed that the acidic sulfonic groups of SPEEK interacted with organic/inorganic clays and as a result of partial barrier the ionic conductivity was decreased but power densities were increased. SPEEK-Cloisite® 30B composite membrane has given 40 mW/cm2 power density value which is higher than pure SPEEK membrane (35 mW/cm2). The proton conductivities of the final composite membranes were close to bare SPEEK membranes which are 0,065 and 0,075 S/cm for SPEEK-Cloisite ® 30B and pristine SPEEK, respectively.  相似文献   

6.
Air-breathing high-temperature proton exchange membrane fuel cell (HT-PEMFC) gets rid of the cumbersome air supplying systems and avoids the water flooding problem by directly exposing the cathode to air and operating the fuel cell at elevated temperature. Performance of the air-breathing HT-PEMFC is dependent on many factors particularly the cathode flow field configurations. However, studies about air-breathing HT-PEMFCs are quite limited in the literature. In the present study, an experimental testing system was setup for the performance measurement of the air-breathing HT-PEMFC. A 3D numerical model was established and validated by the experimental data. Effects of the cathode flow field configurations including the opening shape, end plate thickness, open ratio and opening direction on performance of the air-breathing HT-PEMFC were experimentally and numerically investigated. It was found that the cathode end plate thickness and upward or sideways orientation have the least effect on the performance. The maximum power density of 160 mW/cm2 at the current density of 394 mA/cm2 can be achieved for the cathode flow field with slot holes and an open ratio of 75%.  相似文献   

7.
The zwitterion-coated polyamidoamine (ZC-PAMAM) dendrimer with ammonium and sulfonic acid groups has been synthesized and used as filler for the preparation of PBI-based composite membranes for direct methanol fuel cells. Polybenzimidazole (PBI)/ZC-PAMAM dendrimer composite membranes were prepared by casting a solution of PBI and ZC-PAMAM dendrimer, and then evaporating the solvent. The presence of ZC-PAMAM dendrimer was confirmed by FT-IR and energy-dispersive X-ray spectroscopy (EDS) mapping of sulfur and oxygen elements. The water uptake, swelling degree, proton conductivity, and methanol permeability of the membranes increased with the ZC-PAMAM dendrimer content. For the PBI/ZC-PAMAM-20 membrane with 20 wt% of ZC-PAMAM, it shows a proton conductivity of 1.83 × 10−2 S/cm at 80 °C and a methanol permeability of 5.23 × 10−8 cm2 s−1. Consequently, the PBI/ZC-PAMAM-20 demonstrates a maximum power density of 26.64 mW cm−2 in a single cell test, which was about 2-fold higher than Nafion-117 membrane under the same conditions.  相似文献   

8.
A high temperature-proton exchange membrane fuel cells (HT-PEMFC) based on phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane is able to operate at elevated temperature ranging from 100 to 200 °C. Therefore, it is evident that the relative humidity (RH) of gases within a HT-PEMFC must be minimal owing to its high operating temperature range. However, it has been continuously reported in the literature that a HT-PEMFC performs better under higher inlet RH conditions. In this study, inlet RH dependence on the performance of a HT-PEMFC is precisely studied by numerical HT-PEMFC simulations. Assuming phase equilibrium between membrane and gas phases, we newly develop a membrane water transport model for HT-PEMFCs and incorporate it into a three-dimensional (3-D) HT-PEMFC model developed in our previous study. The water diffusion coefficient in the membrane is considered as an adjustable parameter to fit the experimental water transport data. In addition, the expression of proton conductivity for PA-doped PBI membranes given in the literature is modified to be suitable for commercial PBI membranes with high PA doping levels such as those used in Celtec® MEAs. Although the comparison between simulations and experiments shows a lack of agreement quantitatively, the model successfully captures the experimental trends, showing quantitative influence of inlet RH on membrane water flux, ohmic resistance, and cell performance during various HT-PEMFC operations.  相似文献   

9.
A composite membrane composed of a sulfonated diblock copolymer (SDBC) based on poly(ether ether ketone) blocks copolymerized with partially fluorinated poly(arylene ether sulfone) and sulfonated carbon nanotubes (SCNTs) was fabricated by simple solution casting. Addition of the SCNT filler enhanced the water absorption and proton conductivity of membranes because of the increased per‐cluster volume of sulfonic acid groups, at the same time reinforced the membranes' thermal and mechanical properties. The SDBC/SCNT‐1.5 membrane exhibited the most improved physicochemical properties among all materials. It obtained a proton conductivity of 10.1 mS/cm at 120°C under 20% relative humidity (RH) which was 2.6 times more improved than the pristine membrane (3.9 mS/cm). Moreover, the single cell performance of the SDBC/SCNT‐1.5 membrane at 60°C and 60% RH at ambient pressure exhibited a peak power density of 171 mW/cm2 at a load current density of 378 mA/cm2, while the pristine membrane exhibited 119 mW/cm2 at a load current density of 294 mA/cm2. Overall, the composite membrane exhibited very promising characteristics to be used as polymer electrolyte membrane in fuel cells operated at intermediate RH.  相似文献   

10.
Various sulfonated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO)-polybenzimidazole (PBI) blend membranes were prepared and investigated as proton exchange membranes (PEMs) for direct methanol fuel cell (DMFC) applications. With increasing PBI content water swelling, ion exchange capacity, proton conductivity and methanol permeability of SPPO-PBI membranes were found to be decreased due to acid-base interactions between sulfonate and the amine groups of the blended components. Among various SPPO-PBI blend membranes, 80:20 wt% was found as the optimum composition, which showed the highest membrane selectivity parameter. Direct methanol-air single fuel cell tests revealed a higher cell efficiency of 11.6% for SPPO80-PBI20 than 10.9% for Nafion®117 at 5 M methanol feed, and also a higher power density of 57.6 mW.cm−2 compared to 39.4 mW.cm−2 for Nafion®117. Transport properties as well as DMFC performance results of SPPO-PBI blend PEMs converge to indicate their potential for DMFC applications.  相似文献   

11.
Polybenzimidazole (PBI) was studied as an ionomer binder at varying ratios (1–7) in a 20–40 wt% Pt–Pd/C cathode-coupled catalyst layer for the oxygen reduction reaction (ORR) in a high-temperature proton exchange membrane fuel cell (HT-PEMFC). Catalytic activity was examined by CV and LSV, while the properties of the catalysts were characterized by FESEM-EDX, N2 adsorption–desorption, XRD and FTIR. The results showed that the distribution of metals on the carbon surface, carbon wall thickness and the interaction between ionomer and coupled catalysts affected the ORR performance. The fabricated membrane electrode assembly with 5:95 PBI: 30 wt% Pt–Pd/C catalyst ratio exhibited the best performance and highest durability for HT-PEMFC at 170 °C, yielding a power density of 1.30 Wcm−2 with 0.02 mgPt/cm Pt loading. This performance of ultra-low metal loading of coupled Pt–Pd/C electrocatalyst with PBI binder was comparable to those reported by other studies, highlighting a promising catalyst for fuel cell application.  相似文献   

12.
Polymer composite membranes are fabricated using poly[2,2'-(m-phenylene)-5,5′-bibenzimidazole] (PBI) as a polymer matrix and imidazole functionalized graphene oxide (ImGO) as a filler material for high temperature proton exchange membrane fuel cell applications. ImGO is prepared by the reaction of o-phenylenediamine with graphene oxide (GO). The compatibility of ImGO with PBI matrix is found to be better than that of GO, and as a result PBI composite membrane having ImGO exhibits improved physicochemical properties and larger proton conductivity compared with pure PBI and PBI composite membrane having GO. For example, PBI composite membrane having 0.5 wt% of ImGO shows enhanced tensile strength (219.2 MPa) with minimal decrease of elongation at break value (28.8%) compared with PBI composite membrane having 0.5 wt% of GO (215.5 MPa, 15.4%) and pure PBI membrane without any filler (181.0 MPa, 34.8%). The proton conductivity of this membrane, at 150 °C under anhydrous condition, is 77.52 mS cm?1.  相似文献   

13.
A high conductivity composite proton-exchange membrane Cs2.5H0.5PMo12O40 (CsPOM)/polybenzimidazole (PBI) for use in hydrogen proton-exchange fuel cells has been prepared. The CsPOM composite membrane is insoluble in water. The composite membrane doped with H3PO4 showed high-proton conductivity (>0.15 S cm−1) and good thermal stability. 31P NMR analysis has suggested the formation of a chemical bond between the CsPOM and PBI in the composite membrane. The performance of the membrane in a high-temperature proton-exchange membrane fuel cell (PEMFC) fueled with hydrogen was better than that with a phosphoric acid-doped PBI membrane under the same conditions and at temperatures greater than 150 °C. The CsPOM/PBI composite would appear to be a promising material for high-temperature PEMFC applications.  相似文献   

14.
Here we report enhanced power generation, faster transient response and longer durability of HT-PEMFC by employing a composite membrane of PBI with reduced graphene oxide (rGO) at an optimum loading of 1%. Easy and low cost synthesis of the composite membranes at different loading of rGO is achieved using methane sulfonic acid (MSA) as solvent that resolves the long-standing issue of poor solubility of PBI in the conventional solvents. Property and performance mapping with respect to rGO loading not only leads to attain the optimum but also identifies the window of feasible operating zone. It is observed that with very low (1%) rGO content, composite PBI membrane (rGO-PBI-1) offers the maximum enhancement of all properties viz water uptake, acid uptake, proton conductivity, ion exchange capacity, acid retention capacity, chemical stability, yield strength, while beyond a threshold/critical loading (~4%) deterioration of electrochemical and mechanical properties occur. Steady state performance analysis reveals almost two times peak power enhancement of HT-PEMFC using rGO-PBI-1 electrolyte membrane at an operating temperature of 170 °C; insitu impedance analysis during fuel cell operation reveals sharp decay in charge transfer resistance. Multiple step response analysis confirms (~2 times) faster transient response of fuel cell using rGO-PBI-1 while compared to that with pristine PBI membrane. Fuel cell stability analysis ensures longer durability of operation with negligible decay in voltage.  相似文献   

15.
A copper chloride (CuCl) electrolyzer that constitutes of composite proton exchange membrane (PEM) that functions at medium-temperature (>100 °C) is beneficial for rapid electrochemical kinetics, and better in handling fuel pollutants. A synthesized polybenzimidazole (PBI) composite membrane from the addition of ZrO2 followed with phosphoric acid (PA) is suggested to overcome the main issues in CuCl electrolysis, including the copper diffusion and proton conductivity. PBI/ZrP properties improved significantly with enhanced proton conductivity (3 fold of pristine PBI, 50% of Nafion 117), superior thermal stability (>600 °C), good mechanical strength (85.17 MPa), reasonable Cu permeability (7.9 × 10−7) and high ionic exchange capacity (3.2 × 10−3 mol g−1). Hydrogen produced at 0.5 A cm−2 (115 °C) for PBI/ZrP and Nafion 117 was 3.27 cm3 min−1 and 1.85 cm3 min−1, respectively. The CuCl electrolyzer efficiency was ranging from 91 to 97%, thus proven that the hybrid PBI/ZrP membrane can be a promising and cheaper alternative to Nafion membrane.  相似文献   

16.
Heteropoly acids have been employed to increase the proton conductivity of phosphoric acid (PA) doped polymer membranes for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). In this work, we develop a new composite membrane based on phosphotungstic acid (PWA) doped polyethersulfone-polyvinylpyrrolidone (PES-PVP) matrix, forming PWA/PES-PVP composite membrane for HT-PEMFCs. The homogeneous distribution of PWA on the PES-PVP membrane enhances its mechanical strength. In addition, there is a strong interaction between PWA and PA that is confirmed experimentally by the attenuated total reflectance Fourier Transform Infrared spectroscopy and semi-empirical quantum mechanics calculation. This enhances not only the PA uptake but also the proton conductivity of the PWA/PES-PVP composite membrane. 1H nuclear magnetic resonance spectroscopy results elucidate that the high proton conductivity of the PA doped PWA/PES-PVP membranes is due to their higher proton content and mobility compared to the pristine PA doped PES-PVP membrane. The best results are observed on the PES-PVP composite membrane with addition of 5 wt% PWA, reaching proton conductivity of 1.44 × 10?1 S cm?1 and a peak power density of 416 mW cm?2 at 160 °C and anhydrous conditions. PWA additives increase the proton conductivity and cell performance, demonstrating significantly positive effects on the acid-base composite membranes for high temperature polymer electrolyte membrane fuel cell applications.  相似文献   

17.
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   

18.
In this study, we elucidated the effects of the addition of various mesoporous silicates (0–20 wt%) to the membranes used for high-temperature proton exchange membrane fuel cells (HT-PEMFCs) on cell performance. Two types of polybenzimidazole (PBI)-based hybrid membranes were prepared by homogeneously dispersing a predetermined amount of MCM-41 or SBA-15 within the PBI matrix. Compared to the pure PBI membrane, those with MCM-41 and SBA-15 exhibited significantly enhanced phosphoric acid doping and better mechanical properties, leading to improved HT-PEMFC performance and reduced acid migration. However, the membranes with 20 wt% silicate showed inferior performance compared to those with 10 wt% silicate. In addition, the membranes with SBA-15 exhibited noticeable aggregation, lower phosphoric acid doping, and greater phosphoric acid migration during the leaching test than did the membranes with MCM-41. Finally, during the short-term durability test, the PBI/MCM-41 (10 wt%) membrane showed the best performance (maximum power density of 310  mW cm?2).  相似文献   

19.
The sulfonated poly(fluorenyl ether ketone)s (SPFEK) membranes doped with SiO2 and dispersed by hydroxypropyl methyl cellulose (HPMC) were prepared and investigated for polymer electrolyte membrane fuel cells (PEMFCs) used at high temperature and low relative humidity (RH). The above membrane was prepared by solution dispersion of SPFEK and SiO2 using HPMC as dispersant. The physio-chemical properties of the hybrid membrane were studied by means of scanning electron microscope (SEM), ion-exchange capacity (IEC), proton conductivity, and single cell performance tests. The hybrid membranes dispersed by HPMC were well dispersed when compared with common organic/inorganic hybrid membranes. The hybrid membranes showed superior characteristics as a proton exchange membrane (PEM) for PEMFC application, such as high ionic exchange content (IEC) of 1.51 equiv/g, high temperature operation properties, and the satisfactory ability of anti-H2 crossover. The single cell performances of the hybrid membranes were examined in a 5 cm2 commercial single cell at both 80 °C and 120 °C under different relative humidity (RH) conditions. The hybrid membrane dispersed by HPMC gave the best performance of 260 mW/cm2 under conditions of 0.4 V, 120 °C, 50% RH and ambient pressure. The results demonstrated HPMC being an efficient dispersant for the organic/inorganic hybrid membrane used for PEM fuel cell.  相似文献   

20.
The acid migration in phosphoric acid-doped polybenzimidazole (PBI) membrane high-temperature proton exchange membrane fuel cells (HT-PEMFC) during operation is experimentally evaluated to clarify the influence of the acid balance between the membrane and electrodes on cell performance. A method for controlling the amount of phosphoric acid doped in PBI membranes is investigated, and PBI membranes with various amounts of phosphoric acid are prepared. Cell operation tests and AC impedance spectroscopy of cells fabricated with these membranes are conducted. It was found that the amount of phosphoric acid doped in the membranes can be controlled by changing the solution temperature and the immersion time in phosphoric acid solution. It was also found that the HT-PEMFC performance can be improved by optimizing the amount of phosphoric acid doped in the membrane and by diffusion of phosphoric acid into the catalyst layer during the initial stage of cell operation.  相似文献   

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