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1.
《Journal of power sources》2006,159(2):1015-1024
Various thiol and sultone groups were grafted onto the surface of titanate nanosheets to render organic sulfonic acid (HSO3–) functionality. The nanocomposite membranes were cast together with Nafion® using these materials as inorganic fillers. Nanocomposite membranes containing surface-sulfonated titanates showed higher proton conductivity than composite membranes containing untreated TiO2 P25 particles. They showed better mechanical and thermal stability than Nafion alone. The methanol permeability of nanocomposite membranes decreased with increasing the content of the sulfonated titanate in the nanocomposite membranes. The relative permeability of methanol through these composite membranes with 2 and 5 M methanol solutions was reduced by up to 38 and 26%, respectively, relative to pristine Nafion 115 membranes. The membrane electrode assembly using Nafion/sulfonated titanate nanocomposite membranes exhibited up to 57% higher power density than the assembly containing a pristine Nafion membrane under typical operating conditions of direct methanol fuel cells.  相似文献   

2.
A polymer electrolyte membrane is considered as the heart of fuel cells. Here we report the preparation of proton exchange membranes (PEMs) of poly (vinylidene fluoride) (PVDF) blend poly (methyl methacrylate)-co-poly (sodium-4-styrene sulfonate) (PMMA-co-PSSNa) by solvent evaporation method. Three different types of PEMs have been prepared by using different ratios of PVDF and PMMA-co-PSSNa copolymer. We have investigated the effect of concentration of PVDF on water uptake, ion exchange capacity, mechanical, thermal, and oxidative stability, proton conductivity (Km), and methanol permeability (PM) of the blend membranes. These blend PEMs showed good physicochemical and electrochemical properties along with thermal and oxidative stability. The membrane prepared from PVDF (45% w/w) to PMMA-co-PSSNa (55% w/w) exhibited optimum PM at room temperature (8.38 × 10?7 cm2s?1). This low fuel crossover and high relative selectivity can make our prepared blend membranes a potential candidate in polymer electrolyte membrane fuel cells (PEMFCs) or direct methanol fuel cells (DMFCs).  相似文献   

3.
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   

4.
To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), doubly crosslinked membranes were prepared by chemical crosslinking using bifunctional monomers, such as divinylbenzene (DVB) and bis(p,p-vinyl phenyl) ethane (BVPE), and by radiation crosslinking. The membranes were prepared by grafting of m,p-methylstyrene (MeSt) and p-tert-butylstyrene (tBuSt) into poly(ethylene-co-tetrafluoroethylene) (ETFE) films and subsequent sulfonation. The effects of the DVB and BVPE crosslinkers on the grafting kinetics and the properties of the prepared membranes, such as water uptake, proton conductivity and chemical stability were investigated. Radiation crosslinking was introduced by irradiation of the ETFE base film, the grafted film or the sulfonated membrane. The membrane crosslinked by DVB and BVPE crosslinkers and post-crosslinked by γ-ray irradiation of the corresponding grafted film possessed the highest chemical stability among the prepared membranes, a significantly lower methanol permeability compared to Nafion® membranes, and a better DMFC performance for high methanol feed concentration. Therefore, this doubly crosslinked membrane was promising for application in a DMFC where relatively high methanol concentration could be fed.  相似文献   

5.
Sulfonated branched polymer membranes have been gaining immense attention as the separator in energy‐related applications especially in fuel cells and flow batteries. Utilization of this branched polymer membranes in direct methanol fuel cell (DMFC) is limited because of large free volume and high methanol permeation. In the present work, sulfonated fullerene is used to improve the methanol barrier property of the highly branched sulfonated poly(ether ether ketone sulfone)s membrane without sacrificing its high proton conductivity. The existence of sulfonated fullerene with larger size and the usage of small quantity in the branched polymer matrix effectively prevent the methanol transportation channel across the membrane. The composite membrane with an optimized loading of sulfonated fullerene displays the highest proton conductivity of 0.332 S cm?1 at 80°C. Radical scavenging property of the fullerene improves the oxidative stability of the composite membrane. Composite membrane exhibits the peak power density of 74.38 mW cm?2 at 60°C, which is 30% larger than the commercial Nafion 212 membrane (51.78 mW cm?2) at the same condition. From these results, it clearly depicts that sulfonated fullerene‐incorporated branched polymer electrolyte membrane emerges as a promising candidate for DMFC applications.  相似文献   

6.
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   

7.
The main problem with using membranes in a direct methanol fuel cell is the proton conductivity and methanol permeability that reduces the performance of the membrane. In addition, the cost of the membrane is very high and remains the main issue for the commercialization of Direct Methanol Fuel Cell (DMFC). To solve this problem, this study introduces rice husk ash (RHA) as a bio-filler in sulfonated polyimide (SPI) composite membranes. The bio-filler is expected to reduce the cost of the membrane and at the same time increase the performance of the membrane. In this work, agricultural rice husk waste was subjected to oxidation to produce RHA. The composite membrane displayed maximum values for the ion exchange capacity (0.2829 mmol g−1) and water uptake (55.24%). It was observed that the proton conductivity (0.2058 S cm−1) was higher than that in the pristine SPI membrane. The methanol permeability of the SPI-RHA membranes was reduced to 24 times lower than that of the pristine SPI membrane. In the DMFC passive single-cell test, the maximum power density was increased from 8.0 mW cm−1 to 13.0 mW cm−1 using a composite membrane with 15 wt % RHA. These composite membranes have proven that the addition of RHA enhanced the performances of the fuel cell and have a very high potential to act as an alternative bio-filler for the membranes used in a direct methanol fuel cell.  相似文献   

8.
A type of sulfonated covalent organic framework nanosheets (TpPa-SO3H) was synthesized via interfacial polymerization and incorporated into sulfonated poly (ether ether ketone) (SPEEK) matrix to prepare proton exchange membranes (PEMs). The densely and orderly arranged sulfonic acid groups in the rigid skeleton of the TpPa-SO3H nanosheets, together with their high-aspect-ratio and well-defined porous structure provide proton-conducting highways in the membrane. The doping of TpPa-SO3H nanosheets led to an increased ion exchange capacity up to 2.34 mmol g?1 but a 2-folds reduced swelling ratio, remarkably mitigating the trade-off between high IEC and excessive swelling ratio. Based on the high IEC and orderly arranged proton-conducting sites, the SPEEK/TpPa–SO3H–5 membrane exhibited the maximum proton conductivity of 0.346 S cm?1 at 80 °C, 1.91-folds higher than the pristine SPEEK membrane. The mechanical strength of the composite membrane was also improved by 2.05-folds–74.5 MPa. The single H2/O2 fuel cell using the SPEEK/TpPa–SO3H–5 membrane presented favorable performance with an open voltage of 1.01 V and a power density of 86.54 mW cm?2.  相似文献   

9.
Poly(ether ether ketone) (PEEK) and sulfonated poly(ether ether ketone) (SPEEK, IEC = 2.07 mequiv.g−1) have been synthesized via nucleophilic aromatic substitution reaction. Bromomethylated poly(ether ether ketone) (PEEK-Br) is then prepared and reacted with 2-benzimidazolethiol to obtain the benzimidazole grafted poly(ether ether ketone) (PEEK-BI). The structures of PEEK-Br and PEEK-BI are characterized by 1H NMR spectra. Composite membranes based on SPEEK and PEEK-BI are prepared and their properties used for fuel cells are studied in detail. The results show that the composite membranes exhibit greatly improved mechanical properties as well as reduced water uptake and methanol permeability compared with the pristine SPEEK membrane. The increased oxidative stability and selectivity indicate that the composite membranes are promising to be used as proton exchange membranes.  相似文献   

10.
A series of novel sulfonated poly(ether ether ketone)s containing a cyanophenyl group (SPEEKCNxx) are prepared based on (4-cyano)phenylhydroquinone via nucleophilic substitution polycondensation reactions. To further improve their properties, novel composite membranes composed of sulfonated poly(ether ether ketone)s containing cyanophenyl group as an acidic component and aminated poly(aryl ether ketone) as a basic component are successfully prepared. Most of the membranes exhibit excellent thermal, oxidative and dimensional stability, low-swelling ratio, high proton conductivity, low methanol permeability and high selectivity. The proton conductivities of the membranes are close to Nafion 117 at room temperature. And especially, the values of SPEEKCN40 and its composite membranes are higher than Nafion 117 at 80 °C (0.17 S cm−1 of Nafion, 0.26 S cm−1 of SPEEKCN40, 0.20 S cm−1 of SPEEKCN40-1, and 0.18 S cm−1 of SPEEKCN40-2). Moreover, the methanol permeability is one order magnitude lower than that of Nafion 117. All the data prove that both copolymers and their composite membranes may be potential proton exchange membrane for fuel cells applications.  相似文献   

11.
To solve the conflict between high proton conductivity and low methanol crossover of pristine sulfonated aromatic polymer membranes, the polyorganosilicon doped sulfonated poly (ether ether ketone ketone) (SPEEKK) composite membranes were prepared by introducing polyorganosilicon additive with various functional groups into SPEEKK in this study. Scanning electron microcopy (SEM) images showed the obtained membranes were compact. No apparent agglomerations, cracks and pinholes were observed in the SEM images of composite membranes. The good compatibility between polymer and additive led to the interconnection, thus producing new materials with great characteristics and enhanced performance. Besides, the dual crosslinked structure could be formed in composite membranes through the condensation of silanols and the strong interaction between matrix and additive. The formation of dual crosslinked structure optimized the water absorption, enhanced the hydrolytic stability and oxidative stability of membranes. Especially, the incorporation of additive improved the strength and flexibility of composite membranes at the same time, meaning that the life of the composite membranes might be extended during the fuel cell operation. Meanwhile, the proton conductivity improved with increasing additive content due to the loading of more available acidic groups. It is noteworthy that at 25% additive loading, the proton conductivity reached a maximum value of 5.4 × 10−2 S cm−1 at 25 °C, which exceeded the corresponding value of Nafion@ 117 (5.0 × 10−2 S cm−1) under same experimental conditions. The composite membrane with 20 wt% additive was found to produce the highest selectivity (1.22 × 105 S cm−3) with proton conductivity of 4.70 × 10−2 S cm−1 and methanol diffusion coefficient of 3.85 × 10−7 cm2 s−1, suggesting its best potential as proton exchange membrane for direct methanol fuel cell application. The main novelty of our work is providing a feasible and environment-friendly way to prepare the self-made polyorganosilicon with various functional groups and introducing it into SPEEKK to fabricate the dual crosslinked membranes. This design produces new materials with outstanding performance.  相似文献   

12.
Porous polytetrafluoroethylene (PTFE) membranes were used as support material for sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK)/zirconium sulfophenyl phosphate (ZrSPP)/PTFE composite membranes. The membranes were prepared via a spray painting method. Membranes were characterized by thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). The composite membranes exhibited good thermal stabilities. SEM micrographs confirmed that the pores of the PTFE were filled entirely with SPPESK and ZrSPP. The resulting composite membranes were mechanically durable, dimensionally stable in alternating wet/dry environments, and had lower methanol permeabilities compared with the unsupported SPPESK/ZrSPP composite membranes reported in our previous work. The water uptake of these membranes was also lower than previous SPPESK/ZrSPP composite membranes. The proton conductivity of PTFE supported SPPESK (DS 81%)/ZrSPP(10 wt%) composite membrane was as high as 0.24 S/cm at 120 °C. Thus, the composite membranes exhibited good thermal stabilities, proton conductivities, and good methanol resistance, indicating that these composite membranes could serve as effective alternative membranes for direct methanol fuel cells (DMFCs).  相似文献   

13.
A series of surface functionalized silica submicrospheres by distillation–precipitation polymerization were embedded into chitosan (CS) matrix to fabricate the hybrid membranes for direct methanol fuel cell (DMFC). SEM characterization indicated that the submicrospheres could disperse homogenously within the CS matrix via tuning the polymer/particle and particle/particle interfacial interactions. The incorporation of sulfonated silica and carboxylated silica led to the reduced fractional free volume (FFV), whereas the incorporation of quaternary aminated silica resulted in increased FFV in the hybrid membranes, which was confirmed by the free volume characteristics analysis using positron annihilation lifetime spectroscopy (PALS). The correlation between methanol crossover and FFV was established: the hybrid membranes with lower FFV displayed higher methanol resistance. Meanwhile, the correlation between the proton acceptor/donor capability and proton conductivity in the hybrid membranes was established. Compared with sulfonated silica and quaternary aminated silica, carboxylated silica possessed the optimum matching in proton acceptor and donor capabilities. Therefore, the membrane embedded with carboxylated silica displayed the highest proton conductivity. In particular, embedding carboxylated silica simultaneously reduced the methanol permeability by 63% and increased the proton conductivity by 40% in comparison with pure CS membrane.  相似文献   

14.
Proton transport played a crucial part in the fuel cells, sensors, and batteries. The electrolyte used in fuel cells should possess high proton conductivity and good chemical stability. Herein, taking advantage of the high proton conductivity of metal-organic framework (MOF) and the good chemical stability of branched polymers, a new heterometallic mediated MOF (Zr-Cr-SO3H) is synthesized and utilized as a filler in the highly branched sulfonated polymer (BSP). In addition, Zr-SO3H MOF is also prepared for comparison. Transmission electron microscope study shows that the prepared MOF particles are spherical in size and interconnected through nanosheets. The optimized quantity of MOFs inside the polymer matrix improves the water sorption, mechanical property, and proton conductivity. The composite membranes display an improved open-circuit voltage than the pristine BSP membrane. By comparing the Zr-SO3H MOF incorporated composite membrane, Zr-Cr-SO3H MOF incorporated composite membranes display higher proton conductivity and peak power density in a single-cell test. In particular, the single-cell fabricated with Zr-Cr-SO3H MOF incorporated composite membrane is able to reach the peak power density of 64.6 mWcm−2 at 60°C, which is 26% greater than the Nafion 212 membrane. Furthermore, this work offers a new strategy for the utilization of hetero-metal MOF as a filler for proton exchange membrane applications.  相似文献   

15.
Phosphotungstic acid (HPW) has a good potential as nanofillers in nanocomposite proton exchange membrane with the prerequisite of solving the leakage issue. It is immobilized onto mesoporous graphitic carbon nitride (mg-C3N4) nanosheets surface, and then incorporated into sulfonated poly (aryl ether sulfone) (SPAES) membrane. Structures of the HPW/mg-C3N4 nanocomposites and corresponding SPAES/HPW/mg-C3N4 membranes are characterized by spectroscopic techniques. Fundamental properties and fuel cell performance of the fabricated nanocomposite membranes, and the leakage of HPW are investigated. Along with the highly suppressed HPW leakage, the SPAES/HPW/mg-C3N4 membranes show improved dimensional stability, water affinity and physicochemical stability, as well as better proton conductivity and fuel cell performance. At 80 °C and 60–100% RH, the SPAES/HPW/mg–C3N4–1.5 membrane exhibits 2–3.6 times peak power densities (354.9–584.2 mW/cm2) of the pristine SPAES membrane, and proton conductivity of 203 mS/cm, dimensional change less than 7.5% and weight loss of 1.4% in Fenton oxidation test at 80 °C.  相似文献   

16.
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   

17.
Composite membranes based on sulfonated polyether ether ketone (SPEEK) and hydrated tin oxide (SnO2·nH2O) were prepared and characterized. The formation of the composite substantially modified the properties of SPEEK in terms of durability and electrochemical performance. The structural and electrochemical performance of the samples were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, electrochemical impedance spectroscopy (EIS), water and methanol uptake (WU, MU), and direct methanol fuel cell (DMFC) tests. The polymer electrolyte membrane doped with 50 wt% SnO2·n(H2O) possess good proton transport characteristics, reduced methanol uptake and improved stability with respect to a reference unfilled membrane and it is then suitable for application as electrolyte in DMFCs.  相似文献   

18.
Chitosan is modified by phthaloylation using an excess of phthalic anhydride at 130 °C and blended with the sulfonated polyethersulfone (SPES) to produce composite blend membranes. In particular the introduction of the phthaloyl group into the chitosan matrix increases its solubility in organic solvent, film formability, flexibility, low methanol permeability and with suitable ion conductivity. SPES and N-phthaloyl chitosan (NPHCs) blend membranes with various compositions were prepared and detailed investigation on water uptake, proton conductivity and methanol permeability has been conducted for its suitability in fuel cell environments. Methanol permeability studies envisaged that NPHCs blend membranes are impervious to methanol. The thermograms display the good thermal stabilities of blend membranes than Nafion-117. Relatively high selectivity parameter values of these membranes indicated their greater advantages over Nafion-117 membrane for targeting on fuel cell applications, especially in direct methanol fuel cell (DMFC) environments.  相似文献   

19.
In this paper, the blend membranes based on sulfonated poly(ether ether ketone) and sulfonated cyclodextrin as the proton conducting membranes for DMFCs usage are prepared and investigated. The incorporation of sulfonated cyclodextrin in SPEEK membranes is evaluated by the characteristic absorptions of FT-IR spectra. Thermal stability and micro-morphology of the blend membranes are determined by thermogravimetry analysis and scanning electron microscope tests. The properties of the blend membranes are investigated such as swelling behavior, methanol permeability and proton conduction as function of the fraction of sulfonated cyclodextrin. The methanol crossover could be suppressed by the incorporation of sulfonated cyclodextrin and the methanol permeability decreases when the methanol concentration increases from 2.5 M to 20 M. Proton conduction is also promoted by the introduction of sulfonated cyclodextrin and the proton conductivity increases with the increase of sulfonated cyclodextrin content. The calculated activation energy for proton conduction of the blend membranes is very low and the maximum value is 4.20 kJ mol−1, which is much lower than that of Nafion 115 (9.15 kJ mol−1, measured in our experiments). These data indicate that proton can transport easily through the blend membranes. The selectivity of the blend membranes, a compromise between proton conductivity and methanol permeability, is much higher than that of Nafion 115 at the sulfonated cyclodextrin content above 15 wt.%. The blend membranes with 15, 20, and 25 wt.% of sulfonated cyclodextrin are assembled in the practical DMFCs and their polarization curves with 2.5 M and 8.0 M methanol solution are determined, respectively. The membrane with 20 wt.% sulfonated cyclodextrin reaches the highest power density of 29.52 mW cm−2 at 120 mA cm−2 and 8.0 M methanol solution. These results suggest the potential usage of the SPEEK membranes incorporating with sulfonated cyclodextrin in DMFCs.  相似文献   

20.
In the present study, novel composite membranes were prepared based on sulfonated poly (ether ether ketone)/phosphotungstic acid/carbon nitride nanosheets (SPEEK/HPW/g-C3N4). The alkaline ultrathin g-C3N4 nanosheets in the membranes behaved like “double-sided adhesive”, forming hydrogen bonds with the HPW molecules to anchor hydrophilic HPW without leaking. Moreover, the amine groups of nanosheets formed acid–base pairs with –SO3H of the SPEEK polymer matrix, facilitating the Grotthuss-type transport of proton to improve conductivity. The g-C3N4 inorganic particles provided tortuous pathways for methanol transport to suppress the methanol permeability coefficient. The selectivity of the SPEEK/HPW/g-C3N4-1.0 was 2.3 times higher than that of SPEEK/HPW and 1.5 times higher than that of pristine SPEEK. SPEEK/HPW/g-C3N4 hybrid membranes exhibited stable and durable operation for 240 h under 100% RH at 60 °C. Moreover, membranes exhibited superior mechanical property, with maximum elongation at break of 223.3%.  相似文献   

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