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1.
In direct methanol fuel cells (DMFC), methanol crossover is a major issue which has reduced the performance of polymer electrolyte membrane (PEM) for energy generation. In this study, graphene oxide (GO) and conductive polyaniline decorated GO (PANI-GO) were used as additives in fabrication of sulfonated poly(ether ether ketone) (SPEEK) nanocomposite PEM membrane to reduce methanol crossover. PANI-GO was synthesized by in situ polymerization method and the formation of PANI coated GO nanostructures was confirmed by surface morphology and crystallinity analysis. The membrane morphology and topography analysis confirmed that GO and PANI-GO were well dispersed on the surface of SPEEK membrane. 0.1 wt% PANI-GO modified SPEEK nanocomposite membrane exhibited the highest water uptake and ion exchange capacity of 40% and 1.74 meq g?1, respectively. The oxidative stability of the nanocomposite membranes also improved. Lower methanol permeability of 4.33 × 10?7 cm?2S?1 was noticed for 0.1 wt% PANI-GO modified SPEEK membrane. PANI-GO modified SPEEK membrane enhanced the proton conductivity, which was due to the existence of acidic and hydrophilic group present in PANI and GO. PANI-GO modified SPEEK membrane held higher selectivity of 1.94 × 104 S cm?3 s?1. Overall, these studies revealed that PANI-GO modified SPEEK membrane is a potential material for DMFC applications.  相似文献   

2.
The major risk of using carbon nanotubes (CNTs) to modify proton exchange membranes (PEMs) in fuel cells is possible short‐circuiting due to the excellent electrical conductivity of CNTs. In this article, silica‐coated CNTs (SiO2@CNTs) were successfully prepared by a simple sol–gel process and then used as a new additive in the preparation of sulfonated poly (ether ether ketone) (SPEEK)‐based composite membranes. The insulated and hydrophilic silica coated on the surface of CNTs not only eliminated the risk of short‐circuiting, but also enhanced the interfacial interaction between CNTs and SPEEK, and hence promoted the homogeneous dispersion of CNTs in the SPEEK matrix. Moreover, compared to the methanol permeability of the pure SPEEK membrane (3.42 × 10?7 cm2 s?1), the SPEEK/SiO2@CNT composite membrane with a SiO2@CNT loading of 5 wt% exhibits almost one order of magnitude decrease of methanol crossover, while the proton conductivity still remained above 10?2 S cm?1 at room temperature. The obtained results expose the possibility of SPEEK/SiO2@CNT membranes to be served as high‐performance PEMs in direct methanol fuel cells. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
Sulfonated poly(ether ether ketone) (PEEK) was prepared by sulfonation of commercial Victrex@ PEEK and degree of sulfonation was found to be about 44.5% by 1H NMR. Sulfonated PEEK/polyaniline composite membranes, in order to prevent methanol crossover, were prepared by chemical polymerization of a thin layer of polyaniline (PANI) in the presence of a high oxidant concentration on a single face modification. FTIR and PANI coating density studies confirmed the loading of PANI in sulfonated PEEK membrane matrix. PANI composite membranes with different polymerization time were prepared and subjected to thermogravimetric analysis as well as electrochemical and methanol permeability study to compare with sulfonated PEEK and Nafion 117 membrane. Ion-exchange capacity, water uptake, proton transport numbers and proton conductivities for different PANI composite sulfonated PEEK (SPEEK) membranes were found to be dependent on the coating density of the PANI in the membrane matrix and were slightly lower than that of Nafion 117 membrane. Methanol permeability of these membranes (especially SPEEK/PANI-1.5) was about four times lower than Nafion 117 membrane. Among the all SPEEK membranes synthesized in this study, SPEEK-1.5 appears to be more suitable for direct methanol fuel cell (DMFC) application considering optimum physicochemical and electrochemical properties, thermal stability as well as very low methanol permeability. Above all, the cost-effective and simple fabrication technique involved in the synthesis of such composite membranes makes their applicability quite attractive.  相似文献   

4.
Three kinds of sulfonated poly(ether ether ketone) (SPEEK)/nano oxide (Al2O3, SiO2, and TiO2) composite membranes are fabricated for vanadium redox flow battery (VRFB) application. The composite membranes with 5 wt% of Al2O3, SiO2, and TiO2 (S/A-5 %, S/S-5 %, and S/T-5 %) exhibit excellent cell performance in VRFB. Incorporation of nano oxides (Al2O3, SiO2, and TiO2) in SPEEK membrane improves in aspect of thermal, mechanical, and chemical stabilities due to the hydrogen bonds’ interaction between SPEEK matrix and nano oxides. The energy efficiencies (EEs) of composite membranes are higher than that of Nafion 117 membrane, owing to the good balance between proton conductivity and vanadium ion permeability. The discharge–capacity retentions of composite membranes also overwhelm that of Nafion 117 membrane after 200 cycles, indicating their good stability in VRFB system. These low-cost SPEEK/nano oxide composite membranes exhibit great potential for the application in VRFB.  相似文献   

5.
Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm2 is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm2 with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.  相似文献   

6.
This paper reports proton and methanol transport behavior of composite membranes prepared for use in the direct methanol fuel cell (DMFC). The composite membranes were prepared by embedding various proportions (10–30 wt.%) of inorganic proton conducting material (tungstophosphoric acid (TPA)/MCM-41) into sulfonated poly(ether ether ketone) (SPEEK) polymer matrix. The results indicate that the proton conductivity of the membranes increases with increasing loading of solid proton conducting material. The highest conductivity value of 2.75 mS/cm was obtained for the SPEEK composite membrane containing 30 wt.% solid proton conducting material (50 wt.% TPA in MCM-41). The methanol permeability and crossover flux were also found to increase with increasing loading of the solid proton conducting material. Lowest permeability value of 5.7 × 10−9 cm2 s−1 was obtained for composite membrane with 10 wt.% of the solid proton conducting material (40 wt.% TPA in MCM-41). However, all the composite membranes showed higher selectivity (ratio between the proton conductivity and the methanol permeability) compared to the pure SPEEK membrane. In addition, the membranes are thermally stable up to 160 °C. Thus, these membranes have potential to be considered for use in direct methanol fuel cell.  相似文献   

7.
The ion exchange membrane using polysulfone (PSf) and polyether ether ketone (PEEK) as a basic material was prepared to apply in the polymer electrolyte membrane electrolysis (PEME). The sulfonated block copolymer of PSf and poly(phenylene sulfide sulfone) (SPSf-co-PPSS) and the sulfonated PEEK (SPEEK) were blended with tungstophosphoric acid (TPA) to avoid water swelling at elevated temperatures led to decrease in mechanical strength. These prepared ion exchange membranes showed some interesting characteristics including physicochemical stabilities, mechanical and membrane properties.The prepared ion exchange membrane was utilized to prepare the membrane electrode assembly (MEA). MEA consisted of Pt/PEM/Pt was prepared by equilibrium and non-equilibrium impregnation–reduction (I–R) methods. The prepared MEA by non-equilibrium I–R method was used in the PEME unit cell. The cell voltages of the MEA using SPSf-co-PPSS/TPA and SPEEK/TPA membranes were 1.83 V and 1.90 V at 1 A/cm2 and 80 °C, with platinum loadings of 1.12 and 1.01 mg/cm2, respectively.  相似文献   

8.
Modification of sulfonated poly(ether ether ketone) (SPEEK) membrane was attempted by blending charged surface modifying macromolecule (cSMM). The modified membrane was tested for direct methanol fuel cell (DMFC) application; i.e. a SPEEK/cSMM blend membrane was compared to a SPEEK membrane and a Nafion 112 membrane for the thermal and mechanical stability, methanol permeability, and proton conductivity. Thermal and mechanical stability of the blended membrane were slightly reduced from the SPEEK membrane but still higher than the Nafion 112 membrane. The blend membrane was found to be promising for DMFC applications because of its lower methanol diffusivity (2.75 × 10−7 cm2 s−1) and higher proton conductivity (6.4 × 10−3 S cm−1), than the SPEEK membrane. A plausible explanation was given for the favorable effect of cSMM blending.  相似文献   

9.
A series of sulfonated poly(ether ether ketone)/monoethanolamine/adipic acid (SPEEK/MEA/AA) composite membranes are prepared and investigated to assess their possibility as proton exchange membranes in direct methanol fuel cells (DMFCs). A preliminary evaluation shows that introducing MEA and AA into SPEEK matrix decreases the thermal stability of membrane. However, the degradation temperatures are still above 260 °C, satisfying the requirement for fuel cell operation. Compared with the pure SPEEK membrane, the composite membranes exhibit not only lower water uptake and swelling ratios but also better mechanical property and oxidative stability. Noticeably, the methanol diffusion coefficient of the composite membranes decrease significantly from 3.15 × 10?6 to 0.76 × 10?6 cm2/s with increasing MEA and AA content, accompanied by only a small sacrifice in proton conductivity. Although both the methanol diffusion coefficient and the proton conductivity of composite membranes are lower than those of pure SPEEK and Nafion® 117 membranes, their selectivity (conductivity/methanol diffusion coefficient) are higher. In addition, the composite membranes show excellent stability in aqueous methanol solution. The good thermal and chemical stability, low swelling ratio, excellent mechanical property, low methanol diffusion coefficient, and high selectivity make the use of these composite membranes in DMFCs quite attractive. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2871–2879, 2007  相似文献   

10.
Partially sulfonated poly(etheretherketone) (SPEEK) samples were prepared by modification of corresponding poly(etheretherketone) (PEEK) with concentrated sulfuric acid. Membranes cast from these materials were evaluated as polymer electrolytes for direct methanol fuel cells (DMFCs). SPEEK membranes were characterized by 1H NMR, FT-IR and TGA. The transverse proton conductivities increased from 4.1 to 9.3 × 10−3 S/cm with the increase of the degree of sulfonation (DS) from 0.59 to 0.93. These values were comparable with that of Nafion 117 membrane (1.0 × 10−2 S/cm) measured under the same condition. Nearly one order magnitude difference between transverse conductivity and longitudinal conductivity was found. The methanol permeabilities of the SPEEK membranes were all lower than that of Nafion 117 membrane. The effects of temperature and methanol concentration on the methanol permeability were also studied. In addition, the selectivities of the SPEEK membranes for protons and methanol were all higher than that of Nafion 117 membrane.  相似文献   

11.
A series of highly proton conductive electrolyte membranes with improved methanol barrier properties are prepared from polyallylamine hydrochloride (PAH) and polystyrene sulfonic acid (PSS) including salt by Layer-by-Layer (LbL) method. The effects of added salt type (NaCl, MgCl2) and salt concentration (1.0 M, 0.1 M) on proton conductivity (σ) and methanol barrier properties of the LbL self-assembled composite membranes are discussed in terms of controlled layer thickness and charge density. Furthermore, the influences of ion type in the multilayered composite membranes are studied in conjunction with physicochemical and thermal properties.The deposition of the self-assembly of PAH/PSS film on Nafion is followed by UV–Vis spectroscopy and it is observed that the polyelectrolyte layers growth on both sides of Nafion membrane regularly. (PAH/PSS)5–Na+ and (PAH/PSS)5–H+ with 1.0 M NaCl exhibits 49.6 and 27.8% reduction in lower methanol permittivity in comparison with the pristine Nafion®117, respectively, while the proton conductivities are 12.97 and 74.69 mS cm−1. Promisingly, it is found that the membrane selectivity values (Φ) of all multilayered membranes in H+ form are much higher than that of salt form (Na+ and Mg2+) and perfluorosulfonated ionomers reported in the literature. Also, we find out that the use of polyelectrolytes with high charge density causes a further improvement in proton conductivity and methanol barrier properties simultaneously. These encouraging results indicate that upon a suitable choice of LbL deposition conditions, composite membranes exhibiting both high proton conductivity and improved methanol barrier properties can be tailored for fuel cells.  相似文献   

12.
A series of ionically crosslinked composite membranes were prepared from sulfonated poly(arylene ether sulfone) (SPAES) and polybenzimidazole (PBI) via in situ polymerization method. The structure of the pristine polymer and the composite membranes were characterized by FT-IR. The performance of the composite membranes was characterized. The study showed that the introduction of PBI led to the reduction of methanol swelling ratio and the increase of mechanical properties due to the acid–base interaction between the sulfonic acid groups and benzimidazole groups. Moreover, the oxidative stability and thermal stability of the composite membranes were improved greatly. With the increase of PBI content, the methanol permeability coefficient of the composite membranes gradually decreased from 1.59 × 10−6 cm2/s to 1.28 × 10−8 cm2/s at 30 °C. Despite the fact that the proton conductivity decreased to some extent as a result of the addition of PBI, the composite membrane with PBI content of 5 wt.% still showed a proton conductivity of 0.201 S/cm at 80 °C which could actually meet the requirement of proton exchange fuel cell application. Furthermore, the composite membranes with PBI content of 2.5–7.5 wt.% showed better selectivity than Nafion117 taking into consideration the methanol swelling ratio and proton conductivity comprehensively.  相似文献   

13.
Nanostructured iron–titanium mixed oxides with different Fe/Ti ratios were prepared by sol–gel methods under different preparative conditions. When equal molar amounts of Fe and Ti ions were employed, the product calcined at 500 °C showed an X-ray diffraction pattern that resembles Fe2Ti3O9. On the other hand, lower Fe/Ti ratios favored the formation of Fe2TiO5 while higher ratios resulted in free α-Fe2O3 and TiO2. Besides the effect of the Fe/Ti ratio, the composition of the final product was dependent on the preparative conditions and the calcination temperature. Enhancing the gelation process by heating or by employing an acid catalyst favored the formation of Fe2TiO5 at relatively low temperatures. Compared with the corresponding pure oxides, the prepared iron–titanium mixed oxides showed modified textural characteristics which were also dependent on the composition and the calcination temperature. The mixed oxides showed higher catalytic activity in the oxidation of methanol than their corresponding pure oxides with a noticeable enhanced oxidation potential forming methyl formate and carbon dioxide.  相似文献   

14.
We report that glass–ceramic Li2S–P2S5 electrolytes can be prepared by a single step ball milling (SSBM) process. Mechanical ball milling of the xLi2S·(100 − x)P2S5 system at 55 °C produced crystalline glass–ceramic materials exhibiting high Li-ion conductivity over 10−3 S cm−1 at room temperature with a wide electrochemical stability window of 5 V. Silicon nanoparticles were evaluated as anode material in a solid-state Li battery employing the glass–ceramic electrolyte produced by the SSBM process and showed outstanding cycling stability.  相似文献   

15.
A synthetic method is described to produce a proton conductive polymer membrane with a polynorbornane backbone and inorganic–organic cyclic phosphazene pendent groups that bear sulfonic acid units. This hybrid polymer combines the inherent hydrophobicity and flexibility of the organic polymer with the tuning advantages of the cyclic phosphazene to produce a membrane with high proton conductivity and low methanol crossover at room temperature. The ion exchange capacity (IEC), the water swelling behavior of the polymer, and the effect of gamma radiation crosslinking were studied, together with the proton conductivity and methanol permeability of these materials. A typical membrane had an IEC of 0.329 mmol g−1 and had water swelling of 50 wt%. The maximum proton conductivity of 1.13 × 10−4 S cm−1 at room temperature is less than values reported for some commercially available materials such as Nafion. However the average methanol permeability was around 10−9 cm s−1, which is one hundred times smaller than the value for Nafion. Thus, the new polymers are candidates for low-temperature direct methanol fuel cell membranes.  相似文献   

16.
《Solid State Sciences》2012,14(6):677-681
The polyaniline/TiO2/graphene oxide (PANI/TiO2/GO) composite, as a novel supercapacitor material, is synthesized by in situ hydrolyzation of tetrabutyl titanate and polymerization of aniline monomer in the presence of graphene oxide. The morphology, composition and structure of the composites as-obtained are characterized by SEM, TEM, XRD and TGA. The electrochemical property and impedance of the composites are studied by cyclic voltammetry and Nyquist plot, respectively. The results show that the introduction of the GO and TiO2 enhanced the electrode conductivity and stability, and then improved the supercapacitive behavior of PANI/TiO2/GO composite. Significantly, the electrochemical measurement results show that the PANI/TiO2/GO composite has a high specific capacitance (1020 F g−1 at 2 mV s−1, 430 F g−1 at 1 A g−1) and long cycle life (over 1000 times).  相似文献   

17.
TiO2–carbon nanotube (CNT) heterojunction arrays on Ti substrate were fabricated by a two-step thermal chemical vapor deposition (CVD) method. CNT arrays were first grown on Ti substrate vertically, and then a TiO2 layer, whose thickness could be controlled by varying the deposition time, was deposited on CNTs. Measured by electrochemical impedance spectroscopy (EIS), the thickness of the TiO2 layer could affect the photoresponse ability significantly. About 100 nm thickness of the TiO2 layer proved to be best for efficient charge separation among the tested samples. The optimized TiO2–CNT heterojunction arrays displayed apparently higher photoresponse capability than that of TiO2 nanotube arrays which was confirmed by surface photovoltage (SPV) technique based on Kelvin probe and EIS. In the photocatalytic experiments, the kinetic constants of phenol degradation with TiO2–CNT heterojunctions and TiO2 nanotubes were 0.75 h−1 (R2 = 0.983) and 0.39 h−1 (R2 = 0.995), respectively. At the same time, 53.7% of total organic carbon (TOC) was removed with TiO2–CNT heterojunctions, while the removal of TOC was only 16.7% with TiO2 nanotubes. These results demonstrate the super capability of the TiO2–CNT heterojunction arrays in photocatalysis with comparison to TiO2-only nanomaterial.  相似文献   

18.
Microporous SiO2 and SiO2/MO2 (M=Ti, Zr, Al; 10 mol% MOx) materials for gas separation membrane applications have been prepared from polymeric sols. Characterization of these sols with SAXS showed that the mean fractal dimension of the SiO2 sols is 1.3–1.4 with a radius of gyration of approximately 2.5 nm. The dried and calcined films are microporous and the pore size distribution was bimodal with maxima at diameters of 0.5 nm and 0.75 nm. For the SiO2/TiO2, SiO2/ZrO2 and SiO2/Al2O3 systems, much milder reaction conditions proved to be necessary to obtain sols with comparable fractal dimensions due to the high reactivity of the Ti/Zr/Al-alkoxides. Microporous supported membranes with molecular sieve-like gas transport properties can be prepared from a relatively wide range of sol structures: from polymers too small to characterize with SAXS to structures with fractal dimensions: 1<d f<2.04.  相似文献   

19.
Titanium dioxide (TiO2) nanoparticles were assembled on the surface of nanofiltration blend membrane. For settling TiO2 on the membrane surface, two membrane categories were used: (i) unmodified polyethersulfone (PES)/polyimide (PI) blend membrane, and (ii) –OH functionalized PES/PI blend membrane with different concentrations of diethanolamine (DEA). These membranes were radiated by UV light after TiO2 depositing with different concentrations. 15 min immersion in colloidal suspension and 15 min UV irradiation with 160 W lamps were used for modification. The modification resulted in the formation of a photo-catalytic property with enhanced membrane hydrophilicity. The self-assembly of TiO2 nanoparticles was established through coordinance bonds with –OH functional groups on the membrane surface. A comparison between the UV irradiated TiO2 deposited blend membrane and deposited-functionalized blend membranes showed that –OH groups originate excellent adhesion of TiO2 nanoparticles on the membrane surface, increase reversible deposition, and diminish irreversible fouling. The membranes were characterized using SEM, FTIR, EDX, contact angle, cross flow filtration, and antifouling measurements. SEM images show that the presence of –OH groups on the DEA-modified membrane surface is the main parameter for extra uniformly settlement of TiO2 nanoparticles on the membrane surface. This procedure is a superior technique for modification of PES/PI nanofiltration membranes to enhance water flux and minimization membrane fouling.  相似文献   

20.
A concept of preparing high‐temperature proton exchange membranes with layer‐by‐layer (LBL) self‐assembly technique was proposed and the sulfonated polyetheretherketone (SPEEK) and polyurethane (PU) with 200 LBL deposition cycles denoting (SPEEK/PU)200 membrane was prepared in this research. Owing to the strong electrostatic interaction between ? group in SPEEK and ? C? N+ group in PU, (SPEEK/PU)200 membrane with LBL self‐assembly structure showed a favorable structural stability. The phosphoric acid (PA)‐doped (SPEEK/PU)200 membrane showed a higher proton conductivity relative to PA doped SPEEK/PU membrane by solution casting method (SPEEK/PU)200/40%PA membrane possessed a proton conductivity value of 2.90 × 10?2 S/cm at 150 °C under anhydrous conditions. The LBL self‐assembly structure provided a possibility to reduce the negative effect from polymer skeleton blocking charge carrier species even immobilizing protons. Moreover, the (SPEEK/PU)200 membrane presented the particularly noteworthy mechanical property even with PA doping. The tensile stress values at break were 72.8 and 24.1 MPa, respectively, for (SPEEK/PU)200 and (SPEEK/PU)200/40%PA membrane at room temperature, which were obviously higher than the reported values of 15.9 and 2.81 MPa for SPEEK/PU and SPEEK/PU/60%PA membrane. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3446–3454  相似文献   

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