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1.
Polymer electrolyte membranes (PEM) were fabricated by blending of Poly(2,5-benzimidazole) (ABPBI) and Poly(vinylphosphonic acid) (PVPA) at several stoichiometric ratios with respect to monomer repeating units. The characterization of the membranes were carried out by using Fourier-transform infrared spectroscopy (FT-IR) for inter-polymer interactions, scanning electron microscope (SEM) for surface morphology as well as homogeneity and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) for thermal properties. Water uptake measurements were made to investigate the swelling character the blends that was changed with PVPA composition. The spectroscopic measurements and water uptake studies suggested the complexation between ABPBI and PVPA that inhibited dopant exclusion up on swelling in excess water. Proton conductivities of the hydrated and anhydrous samples were measured using impedance spectroscopy. Although the proton conductivity of the blends was lower in the anhydrous state such as 1.8 × 10−6 S/cm at 150 °C for ABPBI:PVPA with (1:2), it increased to 0.004 S/cm for ABPBI:PVPA (1:4) at 20 °C (RH = 50%).  相似文献   

2.
Star copolymers with good film-forming and mechanical properties were in situ synthesized for fabricating proton exchange membranes. The monomers of 3,4-diaminobenzoic acid were first grafted onto glycidyl-polyhedral oligomeric silsesquioxane (G-POSS) cores and then propagated to the poly(2,5-benzimidazole) (ABPBI) chains. The introduction of the star copolymer improves the movement of the ABPBI polymer chains, resulting in a lower internal viscosity and larger free volume that favor increased membrane flatness and absorbilities of water and phosphoric acid molecules, respectively. It was found that the star copolymers with 1.0 wt% of incorporated POSS (ABPBI-1.0POSS) had the best balance of the acid retentivity and film-forming property as well as mechanical properties that are desirable for proton exchange membranes without PA loss operating at high temperatures. The enhanced cell performance characteristics obtained using the ABPBI-1.0POSS-based membranes indicate that star copolymers are promising materials for use in high-temperature proton exchange membrane fuel cells.  相似文献   

3.
A series of promising proton conducting membranes have been synthesized by using poly(vinyl alcohol), with sulfosuccinic acid (SSA) as a cross-linking agent and poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) as proton source, which form a semi-interpenetrating network (semi-IPN) PVA/SSA/PSSA-MA membrane. A bridge of SSA between PVA molecules not only reinforces the network but also provides extra proton conducting paths. PSSA-MA chains trapped in the network were the major sources of protons in the membrane. FT-IR spectra confirmed the success of the cross-linking reaction and molecular interactions between PVA and PSSA-MA. Associated characteristics of a proton conducting membrane including ion-exchange capacity (IEC), proton conductivity and water uptake were investigated. The measured IECs of the membranes increased with increase of PSSA-MA content varying from 20 to 80% and correlated well with the measured uptake water and proton conductivity. The semi-IPN membranes with PSSA-MA over 60% exhibited a higher proton conductivity than Nafion-115 and also a reasonable level of water uptake. Fuel cell performance of membrane electrode assemblies (MEA) was evaluated at various temperatures with H2/air as well as H2/O2 gases under ambient pressure. A power density of 0.7 W cm−2 was obtained for the MEA using PVA/SSA20/PSSA-MA80 membrane using H2/O2 at 50 °C.  相似文献   

4.
Cerium sulfophenyl phosphate (CeSPP), a novel proton conductor, is prepared starting from mixtures of m-sulfophenyl phosphonic acid (msPPA) and ammonium ceric nitrate. The CeSPP samples are combined with poly (2, 5-benzimidazole) (ABPBI) to prepare ABPBI/CeSPP composite membranes by polyphosphoric acid (PPA) hot-pressed method. The ABPBI/CeSPP composite membranes are characterized by X-ray diffraction (XRD) and infrared spectroscopy (IR). Thermogravimetric analysis (TGA) indicates thermal stability of the composite membranes below 200 °C. Scanning electron microscopy (SEM) indicates that CeSPP particles are homogenously dispersed into the composite membranes. Ce, P and S atoms are well illustrated and uniformly distributed in composite membranes via energy-dispersive X-ray spectroscopy (EDX) analysis. The proton conductivity of membrane doped in 38 wt.% CeSPP reaches 0.14 Scm−1 at 180 °C under 100% relative humidity.  相似文献   

5.
In fuel cell technologies, low-temperature proton exchange membrane fuel cells (LT-PEMFC), high-temperature proton exchange membrane fuel cells (HT- PEMFC), and direct methanol fuel cells (DMFC) are gained significant attention as a promising energy system for practical applications. The developments of cost-effective membrane materials with excellent physicochemical properties are indispensable for replacing the high cost of commercial membranes and achieving the higher performance of fuel cell systems. This review focuses on the developments and modifications of cost-effective poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as a cation exchange membrane for LT-PEMFC, HT- PEMFC and DMFC. Notably, this review bridges the understanding of PPO based membranes, current advancements, structure, physicochemical properties and fuel cell performances. Progressive developments and a systematic overview of PPO-based membrane developments are explained in detail in terms of functionalization, blend, composite, acid-base, cross-linking, copolymerization, coated and reinforcement. Moreover, the changes in physicochemical properties and fuel cell performances in the membrane are deeply reviewed. Additionally, the utilization of PPO based membranes in different kinds of redox flow battery systems are reviewed. Overall, this review provides an exclusive vision and perspectives to develop the PPO based advanced, cost-effective, and high-performance membranes for fuel cell technologies and redox flow battery systems.  相似文献   

6.
Poly (aryl hexafluoro sulfone benzimidazole) and poly (aryl hexafluoro ethoxy benzimidazole), termed as PArF6SO2BI and PArF6OBI, are synthesized and characterized systematically. PArF6SO2BI membranes illustrate good chemical stability in terms of oxidative weight loss due to the electron-withdrawing sulfone functional group. PArF6OPBI membranes exhibit weak chemical stability after immersion in Fenton's solution. Many of the membranes show good conductivities. Higher conductivities of 3.26 × 10?2 S cm?1 at 160 °C with 286.8 wt% acid doped level for 3:1 (2.335 mmol of 4,4′-sulfonyldibenzoic acid and 7.005 mmol of 2, 2-bis(4-carboxyphenyl) hexafluoropropane) ratio of PArF6SO2BI and 7.31 × 10?2 S cm?1 with 356.9 wt% for 3:1 ratio of PArF6OBI are observed. PArF6SO2BI and PArF6OPBI membranes exhibit good conductivity, thermal and mechanical stabilities which are crucial requirements for high temperature fuel cells.  相似文献   

7.
A novel strategy for introducing phosphoric acid as the electrolyte into high-temperature polymer electrolyte fuel cells by using acid impregnated catalyst layers instead of pre-doped membranes is presented in this paper. This experimental approach is used for the development of membrane electrode assemblies based on poly(2,5-benzimidazole) (ABPBI) as the membrane polymer. The acid uptake of free-standing ABPBI used for this work amounts to ABPBI × 3.1 H3PO4 which has a specific conductivity of ∼80 mS cm−1 at 140 °C. Rather thick catalyst layers (20% Pt/C, 1 mg Pt cm−2, 40% PTFE as binder, d = 100-150 μm) are prepared on gas diffusion layers with a dense hydrophobic microlayer. After impregnation of the catalyst layers with phosphoric acid and assembling them with a mechanically robust undoped ABPBI membrane a fast redistribution of the electrolyte occurs during cell start-up. Power densities of about 250 mW cm−2 are achieved at 160 °C and ambient pressure with hydrogen and air as reactants. Details of membrane properties, preparation and optimization of gas diffusion electrodes and fuel cell characterization are discussed. We consider our novel approach to be especially suitable for an easy and reproducible fabrication of MEAs with large active areas.  相似文献   

8.
The novel poly(vinyl alcohol)/titanium oxide (PVA/TiO2) composite polymer membrane was prepared using a solution casting method. The characteristic properties of the PVA/TiO2 composite polymer membrane were investigated by thermal gravimetric analysis (TGA), a scanning electron microscopy (SEM), a micro-Raman spectroscopy, a methanol permeability measurement and the AC impedance method. An alkaline direct alcohol (methanol, ethanol and isopropanol) fuel cell (DAFC), consisting of an air cathode based on MnO2/C inks, an anode based on PtRu (1:1) black and a PVA/TiO2 composite polymer membrane, was assembled and examined for the first time. The results indicate that the alkaline DAFC comprised of a cheap, non-perfluorinated PVA/TiO2 composite polymer membrane shows an improved electrochemical performances. The maximum power densities of alkaline DAFCs with 4 M KOH + 2 M CH3OH, 2 M C2H5OH and 2 M isopropanol (IPA) solutions at room temperature and ambient air are 9.25, 8.00, and 5.45 mW cm−2, respectively. As a result, methanol shows the highest maximum power density among three alcohols. The PVA/TiO2 composite polymer membrane with the permeability values in the order of 10−7 to 10−8 cm2 s−1 is a potential candidate for use on alkaline DAFCs.  相似文献   

9.
The quaternized poly(vinyl alcohol)/alumina (designated as QPVA/Al2O3) nanocomposite polymer membrane was prepared by a solution casting method. The characteristic properties of the QPVA/Al2O3 nanocomposite polymer membranes were investigated using thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cell (ADMFC) comprised of the QPVA/Al2O3 nanocomposite polymer membrane were assembled and examined. Experimental results indicate that the DMFC employing a cheap non-perfluorinated (QPVA/Al2O3) nanocomposite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC with 4 M KOH + 1 M CH3OH, 2 M CH3OH, and 4 M CH3OH solutions are 28.33, 32.40, and 36.15 mW cm−2, respectively, at room temperature and in ambient air. The QPVA/Al2O3 nanocomposite polymer membranes constitute a viable candidate for applications on alkaline DMFC.  相似文献   

10.
Commercially available poly(ether ether sulfone), PEES, was directly sulfonated using concentrated sulfuric acid at low temperatures by minimizing degradation during sulfonation. The sulfonation reaction was performed in the temperature range of 5–25 °C. Sulfonated polymers were characterized by FTIR, 1H NMR spectroscopy and ion exchange capacity (IEC) measurements. Degradation during sulfonation was investigated by measuring intrinsic viscosity, glass transition temperature and thermal decomposition temperature of sulfonated polymers. Sulfonated PEES, SPEES, membranes were prepared by solvent casting method and characterized in terms of IEC, proton conductivity and water uptake. The effect of sulfonation conditions on chemical stability of membranes was also investigated via Fenton test. Optimum sulfonation condition was determined to be 10 °C with conc. H2SO4 based on the characteristics of sulfonated polymers and also the chemical stability of their membranes. SPEES membranes exhibited proton conductivity up to 185.8 mS cm−1 which is higher than that of Nafion 117 (133.3 mS cm−1) measured at 80 °C and relative humidity 100%.  相似文献   

11.
The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH3OH fuels are 12.85, 23.72, and 10.99 mW cm−2, respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO2/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.  相似文献   

12.
13.
A high performance poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) (PVA/MMT/PSSA) proton-conducting composite membrane was fabricated by a solution casting method. The characteristic properties of these blend composite membranes were investigated by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, methanol permeability measurement, and the AC impedance method. The ionic conductivities for the composite membranes are in the order of 10−3 S cm−1 at ambient temperature. There are two proton sources used on this novel composite membrane: the modified MMT fillers and PSSA polymer, both materials all contain the -SO3H group. Therefore, the ionic conductivity was greatly enhanced. The methanol permeabilities of PVA/MMT/PSSA composite membranes is of the order of 10−7 cm2 s−1. It is due to the excellent methanol barrier properties of the PVA polymer. The peak power densities of the air-breathing direct methanol fuel cells (DMFCs) with 1M, 2M, 4M CH3OH fuels were 14.22, 20.00, and 13.09 mW cm−2, respectively, at ambient conditions. The direct methanol fuel cell with this composite polymer membrane exhibited good electrochemical performance. The proposed PVA/MMT/PSSA composite membrane is therefore a potential candidate for future applications in DMFC.  相似文献   

14.
A series of semi-interpenetrating network (SIPN) membranes was synthesized by using poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) as a cross-linking agent and poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) as a proton source for direct methanol fuel cell (DMFC) application. A bridge of SSA between PVA molecules not only reinforced the network but also provided extra proton-conducting paths. PSSA-MA chains trapped in the network were the major proton conduction path of the membrane. The SIPN membranes with 80% PSSA-MA (SIPN-80) exhibited a higher proton conductivity value of 2.59 × 10−2 S cm−1 and very low methanol permeability (4.1 × 10−7 cm2 s−1). More specifically, the SIPN membranes exhibited very high selectivity (proton conductivity/methanol permeability). Membrane characteristics such as water uptake, proton conductivity and methanol permeability were evaluated to determine the effect of PVA molecular weights. The SIPN membranes with higher PVA molecular weight were also evaluated using methanol and oxygen gas in a single cell fuel cell at various temperatures. Power density value of over 100 mW cm−2 was obtained for SIPN membrane-based membrane electrode assembly at 80 °C and using commercial binary alloy anode catalysts and 2 M methanol.  相似文献   

15.
The composite cathodes with lanthanum-based iron and cobalt-containing perovskite La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) and Ce0.9Gd0.1O1.95 (GDC) are investigated for solid oxide fuel cell (SOFC) applications at relatively low operating temperatures (700-800 °C). LSCFs with high surface areas of 55 m2g−1 are synthesized via a complex method with inorganic nano dispersants. The fuel cell performances of composite cathodes on anode supported SOFCs are characterized with GDC materials of surface areas of 5 m2g−1 (ULSA-GDC), 12 m2g−1 (LSA-GDC), and 23 m2g−1 (HAS-GDC). The maximum power density of the SOFCs increases from 0.68 Wcm−2 to 1.2 Wcm−2 at 780 °C and 0.8 V as the GDC surface area increases from 5 m2g−1 to 23 m2g−1. The area specific resistance of the porous composite cathodes with a HAS-GDC are 0.467 ohmcm2 at 780 °C and 1.086 ohmcm2 at 680 °C, while these values with an LSA-GDC are 0.543 ohmcm2 and 0.945 ohmcm2, respectively. The best compositions of the porous composite cathodes result from the morphologies of the GDC materials at each temperature due to the formation of an electron-oxygen ion-gas boundary.  相似文献   

16.
We designed and synthesized a poly(ether imide) (PEI) membrane that has good chemical and mechanical stabilities. Alkalized PEI (A-PEI) membrane was fabricated by solution casting of chloromethylated PEI (CM-PEI) followed by quaternization and alkalization. The chemical structure of the synthesized polymers was verified by proton nuclear magnetic resonance (1H NMR) and Fourier-transform infrared spectroscopy (FT-IR). Physiochemical properties of the membrane such as ion exchange capacity, water uptake, and swelling ratio were investigated. The membranes with a high degree of chloromethylation (DC) exhibited elevated hydroxide ion conductivity in range of 6.7–44.2 mS/cm at 90 °C under 100% relative humidity (RH). The hydrophilic-hydrophobic phase separation was verified by atomic force microscope (AFM) and small angle X-ray scattering (SAXS) measurements. Chemical stability was evaluated by measuring the durability of membranes while they were soaked in oxidative and alkaline solutions at 60 °C for 200 h.  相似文献   

17.
Traditional quaternary ammonium (QA)-type anion exchange membranes (AEMs) usually exhibit insufficient alkaline stability, which impede their practical application in fuel cells. To address this issue, a facile method for the simple and accessible preparation of QA-type AEMs with improved alkaline stability was developed in this study. A series of novel AEMs (QPPO-xx-OH) were prepared from commercially available poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and 3-(dimethylamino)-2,2-dimethyl-1-propanol, via a three-step procedure that included bromination, quaternization, and ion exchange. Scanning electron microscopy revealed that dense, uniform membranes were formed. These QPPO-xx-OH membranes exhibited moderate hydroxide conductivities with ranges of 4–15 mS/cm at 30 °C and 12–36 mS/cm at 80 °C. When tested at similar ion exchange capacity (IEC) levels, the IEC retentions of QPPO-xx-OH membranes were 16–22% higher than that of traditional PPO membranes containing benzyltriethylammonium ions, after immersed in 2 M NaOH aqueous solution at 60 °C for 480 h, and the QPPO-47-OH membrane displayed excellent alkaline stability with the IEC retention of 92% after 480 h. In addition, the QPPO-xx-OH membranes also exhibited robust mechanical properties (tensile strength up to 37.6 MPa) and good thermal stability (onset decomposition temperature up to 150 °C). This study provides a new and scalable method for the facile preparation of AEMs with improved alkaline stability.  相似文献   

18.
A series of hydrocarbon membranes consisting of poly(vinyl alcohol) (PVA), sulfosuccinic acid (SSA) and poly(vinyl pyrrolidone) (PVP) were synthesized and characterized for direct methanol fuel cell (DMFC) applications. Fourier transform infrared (FT-IR) spectra confirm a semi-interpenetrating (SIPN) structure based on a cross-linked PVA/SSA network and penetrating PVP molecular chains. A SIPN membrane with 20% PVP (SIPN-20) exhibits a proton conductivity value comparable to Nafion® 115 (1.0 × 10−2 S cm−1 for SIPN-20 and 1.4 × 10−2 S cm−1 for Nafion® 115). Specifically, SIPN membranes reveal excellent methanol resistance for both sorption and transport properties. The methanol self-diffusion coefficient through a SIPN-20 membrane conducted by pulsed field-gradient nuclear magnetic resonance (PFG-NMR) technology measures 7.67 × 10−7 cm2 s−1, which is about one order of magnitude lower than that of Nafion® 115. The methanol permeability of SIPN-20 membrane is 5.57 × 10−8 cm2 s−1, which is about one and a half order of magnitude lower than Nafion® 115. The methanol transport behaviors of SIPN-20 and Nafion® 115 membranes correlate well with their sorption characteristics. Methanol uptake in a SIPN-20 membrane is only half that of Nafion® 115. An extended study shows that a membrane-electrode assembly (MEA) made of SIPN-20 membrane exhibits a power density comparable to Nafion® 115 with a significantly higher open current voltage. Accordingly, SIPN membranes with a suitable PVP content are considered good methanol barriers, and suitable for DMFC applications.  相似文献   

19.
There are several problems which are holding back the use of fuel cells. The utilization of fuel cells depends on the start-up costs which are very high due to the use of expensive materials for their construction. In that respect, we describe a cost-effective alkaline fuel cell (AFC) that uses solid, polymer based, membrane instead of conventionaly used, highly concentrated, corrosive, liquid alkaline electrolyte. This approach to AFC is potentially the basis of a simple, low-cost system, that can solve one of the problems of the highly-efficient and environment-friendly AFC.The focus of this paper are low cost composite alkaline membranes, based on poly(vinyl alcohol) (PVA). The PVA matrix is made by solution cast method and gamma irradiation crosslinking. Three different types of membranes are obtained in this manner - plain PVA membrane, PVA membrane cross-linked using gamma irradiation (γ-PVA) and composite PVA membrane doped with Mo (PVA-Mo). These membranes are immersed in the alkaline solution and investigated as anion exchange membranes. The performance of the solid alkaline fuel cells (SAFCs) containing these PVA membranes has been studied under hydrogen and oxygen gas flow on the Pt/C catalyst. Both, γ-PVA and PVA-Mo membranes are modified to absorb larger amounts of alkaline solution than the PVA membrane, thus greatly improving the performance of the SAFC, in terms of output power. This is clearly indicated in the polarisation curves. The electrochemical impedance spectroscopy measurements during the SAFC operation were also performed to give better insight in the effect observed. Investigation presented in this paper clearly indicates that solid alkaline PVA membranes can be used for the construction of the SAFCs.  相似文献   

20.
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   

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