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1.
Sol–gel derived Nafion/SiO2 hybrid membrane is prepared and employed as the separator for vanadium redox flow battery (VRB) to evaluate the vanadium ions permeability and cell performance. Nafion/SiO2 hybrid membrane shows nearly the same ion exchange capacity (IEC) and proton conductivity as pristine Nafion 117 membrane. ICP-AES analysis reveals that Nafion/SiO2 hybrid membrane exhibits dramatically lower vanadium ions permeability compared with Nafion membrane. The VRB with Nafion/SiO2 hybrid membrane presents a higher coulombic and energy efficiencies over the entire range of current densities (10–80 mA cm−2), especially at relative lower current densities (<30 mA cm−2), and a lower self-discharge rate compared with the Nafion system. The performance of VRB with Nafion/SiO2 hybrid membrane can be maintained after more than 100 cycles at a charge–discharge current density of 60 mA cm−2. The experimental results suggest that the Nafion/SiO2 hybrid membrane approach is a promising strategy to overcome the vanadium ions crossover in VRB.  相似文献   

2.
In our previous work, Nafion/SiO2 hybrid membrane was prepared via in situ sol–gel method and used for the vanadium redox flow battery (VRB) system. The VRB with modified Nafion membrane has shown great advantages over that of the VRB with Nafion membrane. In this work, a novel Nafion/organically modified silicate (ORMOSIL) hybrids membrane was prepared via in situ sol–gel reactions for mixtures of tetraethoxysilane (TEOS) and diethoxydimethylsilane (DEDMS). The primary properties of Nafion/ORMOSIL hybrids membrane were measured and compared with Nafion and Nafion/SiO2 hybrid membrane. The permeability of vanadium ions through the Nafion/ORMOSIL hybrids membrane was measured using an UV–vis spectrophotometer. The results indicate that the hybrids membrane has a dramatic reduction in crossover of vanadium ions compared with Nafion membrane. Fourier transform infrared spectra (FT-IR) analysis of the hybrids membrane reveals that the ORMOSIL phase is well formed within hybrids membrane. Cell tests identify that the VRB with Nafion/ORMOSIL hybrids membrane presents a higher coulombic efficiency (CE) and energy efficiency (EE) compared with that of the VRB with Nafion and Nafion/SiO2 hybrid membrane. The highest EE of the VRB with Nafion/ORMOSIL hybrids membrane is 87.4% at 20 mA cm−2, while the EE of VRB with Nafion and the EE of VRB with Nafion/SiO2 hybrid membrane are only 73.8% and 79.9% at the same current density. The CE and EE of VRB with Nafion/ORMOSIL hybrids membrane is nearly no decay after cycling more than 100 times (60 mA cm−2), which proves the Nafion/ORMOSIL hybrids membrane possesses high chemical stability during long charge–discharge process under strong acid solutions. The self-discharge rate of the VRB with Nafion/ORMOSIL hybrids membrane is the slowest among the VRB with Nafion, Nafion/SiO2 and Nafion/ORMOSIL membrane, which further proves the excellent vanadium ions blocking characteristic of the prepared hybrids membrane.  相似文献   

3.
A series of novel organic-inorganic hybrid membranes with special microstructure, based on sulfonated poly (fluorenyl ether ketone) ionomer (SFPEK, IEC = 1.92 mequiv. g−1) and SiO2 or sulfonic acid group containing SiO2 (SiO2-SO3H), has been successfully designed and prepared for vanadium redox flow battery (VRB) application. The SiO2-SO3H is synthesized by co-condensation of tetraethoxysilane and γ-propyl mercaptotrimethoxysilane via sol-gel process to control the same IEC with neat SPFEK. The hybrid membranes are prepared by simply adding the inorganic particles into the SPFEK solution in N,N′-dimethylacetamide, followed by ultrasonic dispersion, casting and profiled temperature drying process. The morphology is examined by SEM-EDX which is applied to the top surface, bottom surface and cross-section of the hybrid membranes. The water uptake, oxidative stability, thermal property, mechanical property, proton conductivity, VO2+ permeability and single cell performance are investigated in detail in order to understand the relationship between morphology and property of the membranes. All the hybrid membranes show dramatically improved proton selectivity at 20 °C and 40 °C when compared with Nafion117. The VRB assembled with the SPFEK/3%SiO2 and SPFEK/9%SiO2 membranes exhibit higher coulombic efficiency and average discharge voltage than the VRB assembled with the SPFEK membrane at all the tested current densities.  相似文献   

4.
A poly(vinylidene difluoride) (PVDF) membrane was grafted with styrene (St) and maleic anhydride (MAn) using an electron-beam-induced pre-irradiation grafting technique. The grafted membrane (PVDF-g-PS-co-PMAn) was then sulfonated and hydrolyzed to give an ion exchange membrane (denoted as PVDF-g-PSSA-co-PMAc) for vanadium redox flow batteries (VRB) use. Micro-FTIR analysis indicated that PVDF was successfully grafted and sulfonated at the above condition, and the membrane with a high grafting yield (GY) can be easily prepared in a St/MAn binary system at low dose due to a synergistic effect. The water uptake and ion exchange capacity (IEC) of the PVDF-g-PSSA-co-PMAc membrane increased with GY, so too did the conductivity. At a GY of 33.6%, the resulting PVDF-g-PSSA-co-PMAc membrane showed a much higher IEC and conductivity than a conventional Nafion117 membrane, and a much lower permeability of vanadium ions: ca. 1/11 to 1/16 of that through Nafion117. Open circuit voltage measurements showed that the VRB assembled with the PVDF-g-PSSA-co-PMAc membrane maintained values above 1.3 V after a period of 33 h, which was much longer than that with the Nafion117 membrane. It is expected that this work provides a new approach for the fabrication of ion exchange membranes for VRB.  相似文献   

5.
In order to develop novel membranes for vanadium redox flow battery (VRB) with low self-discharge rate and low cost, sulfonated poly(fluorenyl ether ketone) (SPFEK) was synthesized directly via aromatic nucleophilic polycondensation of bisphenol fluorene with 60% sulfonated difluorobenzophenone and 40% difluorobenzophenone. The SPFEK membrane shows the lower permeability of vanadium ions. The open circuit voltage evaluation demonstrates that the SPFEK membrane is superior to Nafion 117 membrane in self-discharge test. Both energy efficiencies (EE) and power densities of the VRB single cell based on the SPFEK membrane are higher than those of the VRB with Nafion 117 membrane at the same current densities. The highest coulombic efficiency (CE) of VRB with SPFEK membrane is 80.3% while the highest CE of the VRB with Nafion 117 membrane is 77.0%. The SPFEK membrane shows the comparative stability to Nafion 117 membrane in VO2+ electrolyte. The experimental results suggest that SPFEK membrane is a promising ion exchange membrane for VRB.  相似文献   

6.
Chitosan (Chs) flakes were prepared from chitin materials that were extracted from the exoskeleton of Cape rock lobsters in South Africa. The Chs flakes were prepared into membranes and the Chs membranes were modified by cross-linking with H2SO4. The cross-linked Chs membranes were characterized for the application in direct methanol fuel cells. The Chs membrane characteristics such as water uptake, thermal stability, proton resistance and methanol permeability were compared to that of high performance conventional Nafion 117 membranes. Under the temperature range studied 20-60 °C, the membrane water uptake for Chs was found to be higher than that of Nafion. Thermal analysis revealed that Chs membranes could withstand temperature as high as 230 °C whereas Nafion 117 membranes were stable to 320 °C under nitrogen. Nafion 117 membranes were found to exhibit high proton resistance of 284 s cm−1 than Chs membranes of 204 s cm−1. The proton fluxes across the membranes were 2.73 mol cm−2 s−1 for Chs- and 1.12 mol cm−2 s−1 Nafion membranes. Methanol (MeOH) permeability through Chs membrane was less, 1.4 × 10−6 cm2 s−1 for Chs membranes and 3.9 × 10−6 cm2 s−1 for Nafion 117 membranes at 20 °C. Chs and Nafion membranes were fabricated into membrane electrode assemblies (MAE) and their performances measure in a free-breathing commercial single cell DMFC. The Nafion membranes showed a better performance as the power density determined for Nafion membranes of 0.0075 W cm−2 was 2.7 times higher than in the case of Chs MEA.  相似文献   

7.
Nafion 117 membranes were modified by in situ chemical polymerization of 3,4-ethylenedioxythiophene using H2O2 as oxidant for direct methanol fuel cell application. Methanol permeability and proton conductivity of the poly(3,4-ethylenedioxythiophene)-modified Nafion membranes as a function of temperature were investigated. An Arrhenius-type dependency of methanol permeability and proton conductivity on temperature exists for all the modified membranes. Compared with Nafion 117 membrane at 60 °C, the methanol permeability of these modified membranes is reduced from 30% to 72%, while the proton conductivity is decreased from 4% to 58%, respectively. Because of low methanol permeability and adequate proton conductivity, the DMFC performances of these modified membranes were better than that of Nafion 117 membrane. A maximum power density of 48.4 mW cm−2 was obtained for the modified membrane, while under same condition Nafion 117 membrane got 37 mW cm−2.  相似文献   

8.
Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test.  相似文献   

9.
The aim of this work is to incorporate inorganic compounds into the Nafion matrix (composite membranes) for high temperature of a polymer electrolyte fuel cell (Tcell > 100 °C). Three silicon oxides having a different morphology were synthesized starting with a tetraethyl orthosilicate as a precursor via sol-gel method: SBA15, SBA15-SH and SiO2. Successively, composite Nafion membranes were prepared using a 3% (w/w) of each powder through a standardized casting method. The influence of SiO2 morphology on chemical-physical properties of the membranes was highlighted resulting in a reduction of the swelling parameters of the composite membranes if compared at T ≥ 80 °C to a recast bare Nafion membrane, used as a reference. Good proton conductivity was also observed for all composite membranes with values of 0.144 S cm−1, 0.136 S cm−1, 0.090 S cm−1and 0.078 S cm−1 recorded at 80 °C (100% RH) for Nrecast, NSBA15, NSBA15-SH and NSiO2, respectively. The polarisation curves carried out at 120 °C (75% RH, 1.5 abs. bar) have revealed a higher stability for NSBA15 membrane after a short time-test, probably because the silica morphology is able to retain water within the polymer matrix and, in accordance to the swelling data.  相似文献   

10.
By immersing Nafion membrane into dopamine aqueous solution under mild conditions, a series of modified Nafion membranes for the application in direct methanol fuel cell (DMFC) were fabricated. High resolution scanning electron microscope and Fourier transform infrared spectra characterization revealed that a dense nano-layer around 50 nm was formed and adhered tightly to Nafion surface. Small-angle X-ray scattering, wide X-ray diffractometer and positron annihilation lifetime spectroscopy analysis implied that the microstructure such as phase-separated structure and ion-cluster channel of Nafion layer was slightly changed after surface modification. The influence of modification conditions including pH value, dopamine concentration and immersing time upon membrane performance was investigated. Due to the effective reduction of methanol dissolution and enhancement of methanol diffusion resistance, the methanol crossover of the modified membranes was dramatically suppressed by about 79% from 3.14 × 10−6 to about 0.65 × 10−6 cm2 s−1. Meanwhile, the proton conductivity of the modified membranes was slightly decreased to be around 0.06 S cm−1. Consequently, the comprehensive performance of the modified membranes was improved by about five times. These results hinted the application promises of such modified Nafion membranes in DMFC.  相似文献   

11.
In this report, a new nanofiller consisting of silica “cores” bearing fluoroalkyl surface functionalities is synthesized and adopted in the preparation of a series of hybrid inorganic-organic proton conducting membranes based on Nafion. The hybrid materials are obtained by a solvent-casting procedure and include between 0 and 10 wt.% of nanofiller. The resulting systems are extensively characterized by Thermogravimetry (TG), Modulated Differential Scanning Calorimetry (MDSC) and Dynamic Mechanical Analysis (DMA), showing that the hybrid materials are stable up to 240 °C and that their overall thermal and mechanical properties are affected both by the polar groups on the surface of the silica “cores” and by the fluoroalkyl surface functionalities of the nanofiller. The electric properties of the hybrid materials are investigated by broadband dielectric spectroscopy (BDS). It is shown that proton conductivity of the materials is not compromised by the lower water uptake arising from the hydrophobic character of the nanofiller. With respect to a pristine Nafion recast membrane, the hybrid material characterized by 5 wt.% of nanofiller, [Nafion/(Si80F)0.7], shows the highest conductivity in all the investigated temperature range (5 ≤ T ≤ 155 °C). Indeed, [Nafion/(Si80F)0.7] features the lowest water uptake and presents a conductivity of 0.083 S cm−1 at 135 °C. This result is consistent with the good performance of the membrane in single fuel cell tests.  相似文献   

12.
Ultrafiltration (UF)-based proton-conductive membranes, which comprised nanosize SiO2, polyethersulfone and aqueous acid absorbed, as an alternative to traditional ion exchange membranes, were first proposed and successfully prepared for H2/Cl2 fuel cell. Various membranes were prepared with different weight fractions of SiO2 nanoparticles. The effect of silicon content on the performance of membranes was characterized. The ionic conductivity of a membrane doped with 3 M hydrochloric acid increased with the silicon content and reached 0.150 S cm−1 at 15 wt.% SiO2. A non-optimized H2/Cl2 fuel cell assembled with the modified UF membrane (115 μm thick) exhibited better performance than that with Nafion 115 membrane. It demonstrated that 12.67% and 55.03% improved at 10 wt.% and 15 wt.% SiO2, respectively. The study provides an effective way to fabricate high performance porous membranes for H2/Cl2 fuel cell application.  相似文献   

13.
In this study, proton conducting Nafion-poly(1-vinyl-1,2,4-triazole) blends are produced. Nafion/polymer blend membranes are prepared by means of film casting from the Nafion-PVTri solutions at several molar ratios of PVTri repeat unit to -SO3H. The chemical structure of the homopolymer PVTri is confirmed by FT-IR and 13C NMR. Thermal properties are investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and the results illustrated that all these Nafion-PVTri electrolytes are thermally stable at least up to 300 °C. The membrane properties are further characterized for their morphology by scanning electron microscopy (SEM) and water uptake measurements. The methanol permeability of these membranes is measured and the results exhibited that they have quite lower methanol permeability compared to pristine Nafion112. The electrochemical properties of PVTri are investigated by cyclic voltammetry. The conductivity of Nafion-P(VTri)1 blend membranes is measured to be 5.3 × 10−4 S cm−1 at 220 °C, in anhydrous state. The conductivity of blend increased at least three orders of magnitude up on hydration, i.e., exceeding 10−3 S cm−1 with RH = 50% at ambient temperature.  相似文献   

14.
An improved solution-cast method is presented to prepare multi-wall carbon nanotubes (MWCNTs)/Nafion® reinforced membrane with different MWCNTs content (from 1 to 4 wt.%). MWCNTs were oxidized by H2O2 and sodium hydroxide (NaOH) was added into the MWCNTs/Nafion®/N,N-dimethylacetamide (DMAC) solution. The long-term stability of the resulting dispersions was much better than the unmodified dispersions. The as-cast membrane was observed by scanning electron microscope (SEM). The MWCNTs were uniformly dispersed in the Nafion® resin. The tensile strength and the elongation at break were greatly improved for the reinforced membranes compared to the recast Nafion® membranes (54 and 27%, respectively). The fuel cell performance of the reinforced membranes with different MWCNTs contents was also tested at 80 °C under fully humidified conditions. By comparing the mechanical properties, proton conductivity and fuel cell performance of the reinforced membranes, we concluded that the content of MWCNTs in the reinforced membranes should not exceed 3 wt.%. The MWCNTs/Nafion® reinforced membrane with 3 wt.% MWCNTs content showed the best mechanical characteristics and excellent fuel cell performance.  相似文献   

15.
In this study, functionalized titania nanotubes (F-TiO2-NT) were synthesized by using 3-mercaptopropyl-tri-methoxysilane (MPTMS) as a sulfonic acid functionalization agent. These F-TiO2-NT were investigated for potential application in high temperature hydrogen polymer electrolyte membrane fuel cells (PEMFCs), specifically as an additive to the proton exchange membrane. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) results confirmed that the sulfonic acid groups were successfully grafted onto the titania nanotubes (TiO2-NT). F-TiO2-NT showed a much higher conductivity than non-functionalized titania nanotubes. At 80 °C, the conductivity of F-TiO2-NT was 0.08 S/cm, superior to that of 0.0011 S/cm for the non-functionalized TiO2-NT. The F-TiO2-NT/Nafion composite membrane shows good proton conductivity at high temperature and low humidity, where at 120 °C and 30% relative humidity, the proton conductivity of the composite membrane is 0.067 S/cm, a great improvement over 0.012 S/cm for a recast Nafion membrane. Based on the results of this study, F-TiO2-NT has great potential for membrane applications in high temperature PEMFCs.  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.
Crystallized zirconia nanoparticles with diameters of 6.3 ± 0.5 nm were in situ formed in Nafion solution through sol–gel process. Nafion molecules were self-assembled onto zirconia nanoparticles through electrostatic interactions and prevent the further growth of initial formed particles. The Nafion–zirconia nanocomposite membranes were formed using a recasting process. It was found that the addition of zirconia nanoparticles did not affect the crystallinity and structure of Nafion in the membrane significantly. The formed Nafion–zirconia nanocomposite membrane shows enhanced water retention ability at 100 °C compared to recast pure Nafion membrane, especially at medium and high relative humidity. This work demonstrates the potential of Nafion–zirconia nanocomposite membranes for PEMFC applications.  相似文献   

18.
Hybrid membranes composed of chitosan (CS) as organic matrix and surface-modified Y zeolite as inorganic filler are prepared and their applicability for DMFC is demonstrated by methanol permeability, proton conductivity and swelling property. Y zeolite is modified using silane coupling agents, 3-aminopropyl-triethoxysilane (APTES) and 3-mercaptopropyl-trimethoxysilane (MPTMS), to improve the organic–inorganic interfacial morphology. The mercapto group on MPTMS-modified Y zeolite is further oxidized into sulfonic group. Then, the resultant surface-modified Y zeolites with either aminopropyl groups or sulfonicpropyl groups are mixed with chitosan in acetic acid solution and cast into membranes. The transitional phase generated between chitosan matrix and zeolite filler reduces or even eliminates the nonselective voids commonly exist at the interface. The hybrid membranes exhibit a significant reduction in methanol permeability compared with pure chitosan and Nafion117 membranes, and this reduction extent becomes more pronounced with the increase of methanol concentration. By introducing –SO3H groups onto zeolite surface, the conductivity of hybrid membranes is increased up to 2.58 × 10−2 S cm−1. In terms of the overall selectivity index (β = σ/P), the hybrid membrane is comparable with Nafion117 at low methanol concentration (2 mol L−1) and much better (three times) at high methanol concentration (12 mol L−1).  相似文献   

19.
The paper is concerned with the formation of Layer-by-Layer (LbL) self-assembly of highly charged polyvinyl sulfate potassium salt (PVS) and polyallylamine hydrochloride (PAH) on Nafion membrane to obtain the multilayered composite membranes with both high proton conductivity and methanol blocking properties. Also, the influences of the salt addition to the polyelectrolyte solutions on membrane selectivity (proton conductivity/methanol permeability) are discussed in terms of controlled layer thickness and charge density.The deposition of the self-assembly of PAH/PVS is confirmed by SEM analysis and it is observed that the polyelectrolyte layers growth on each side of Nafion membrane regularly. (PAH/PVS)10-Na+ and (PAH/PVS)10-H+ with 1.0 M NaCl provide 55.1 and 43.0% reduction in lower methanol permittivity in comparison to pristine Nafion, respectively, while the proton conductivities are 12.4 and 78.3 mS cm−1. Promisingly, it is found that the membrane selectivity values (Φ) of all multilayered composite membranes in H+ form are much higher than those of Na+ form and perfluorosulfonated ionomers reported in the literature. These encouraging results indicate that composite membranes having both superior proton conductivity and improved methanol barrier properties can be prepared from highly charged polyelectrolytes including salt for fuel cell applications.  相似文献   

20.
Novel sulfonated poly (fluorenyl ether ketone) with pendant quaternary ammonium groups (SPFEKA) was successfully synthesized by one-pot copolymerization of bis(4-fluoro-3-sulfophenyl)sulfone disodium salt, 4,4′-difluorobenzophenone, bisphenol fluorene and 2,2′-dimethylaminemethylene-9,9′-bis(4-hydroxyphenyl) fluorene (DABPF). The chemical structures were confirmed by FT-IR, and 1H NMR. The thermal properties were fully investigated by TGA. The synthesized copolymers SPFEKAs are soluble in aprotic solvents, and can be cast into membranes on a glass plate from their N,N′-dimethylacetamide (DMAc) solution. A new kind of amphoteric ion exchange membrane (AIEM) was obtained by immersed SPFEKA into 1 M sulfuric acid. The proton conductivities of these membranes are comparable to the most reported sulfonated polymers under the same conditions. The permeability of vanadium ions in vanadium redox flow battery (VRB) was effectively suppressed by introducing quaternary ammonium groups for Donnan exclusion effect. AIEM-20% possess a only 4.4% vanadium ion permeability of Nafion 115. Cell performance tests showed that the VRB assembled with AIEM-20% shows the highest coulombic efficiency (CE) at the current density of 50 mA/cm2, because of its lowest VO2+ permeability. In conclusion, these ionomers could be promising candidates for ion-exchange membranes for VRB applications.  相似文献   

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