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1.
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   

2.
A series of proton exchange electrolytes were synthesized by blending polystyrene sulfonic acid (PSSA) functionalized ZWP ion exchanger and sulfonated poly(vinylidene fluoride) (SPVDF) as base by using solution casting method. The poly(vinylidene fluoride) was sulfonated by employing a direct sulfonation technique demonstrated in the literature. Surface modification of the ZWP was done to obtain the PSSA-ZWP ion exchanger. The membranes were synthesized by using ZWP and PSSA-ZWP as ion exchangers in the SPVDF polymer matrix. The physicochemical characterization of the membranes was performed by using FT-IR and XRD. The scanning electron microscope (SEM) was used to investigate the surface morphology of the fabricated membranes for any possible defects. Important membrane parameters, such as water uptake (up to 26%), methanol uptake (up to 22%), chemical stability (7.4%) and mechanical stability (tensile strength of up to 44 MPa), were measured and are reported. The ion exchange capacity (max 0.62 meq g?1) and electrochemical characterization of the membranes was conducted and parameters such as transport number (max 0.84) indicating good ion selectivity of the membranes and proton conductivity (max 3.89 mS/cm) were also determined. The single cell DMFC performance of the SPVDF-ZWP-PSSA membrane was evaluated at three different operating temperatures of 30 °C, 60 °C and 90 °C, out of which the synthesized membrane performed best at 60 °C with maximum current density and power density of 49.8 mAcm?2 and 20.1 mWcm?2 respectively.  相似文献   

3.
DMFC received great consideration since it was developed due to its efficiency in electricity production and easy start-up and process. The selectivity of sodium alginate-based membrane as a function of sulfonated graphene oxide and glycerol content is analysed using response surface methodology. It is observed that the properties of the membrane are strongly influenced by the glycerol and sulfonated graphene oxide loading in order to produce the optimum morphology and conducting properties, thus affecting the selectivity of the membrane and consequently the overall performance of the direct methanol fuel cell. The objective of this study is to determine the parameters that significantly affecting the performance of the membrane. Two parameters were taken into consideration that is the weight percentage of sulfonated graphene oxide and glycerol loadings. Both are determined approximately 0.5 wt% to 5 wt% and 0.5 ml–6.0 ml, respectively. The best selectivity result is achieved by using SA/SGO biomembrane with loadings of 2.78 wt% SGO and 3.11 ml of glycerol, respectively. The selectivity is determined as 12.956 × 104 S scm?3. This study proves that the sulfonated graphene oxide and glycerol improved the final membrane structures and performances of the membrane based on numerical analysis, the observation from field emission scanning electron microscopy, atomic force microscope structural analysis as well as the performance of direct methanol fuel cell.  相似文献   

4.
Novel 4,4′-dihydroxy-α-methylstilbene (HMS)-based sulfonated poly(arylene ether sulfone) with sulfonic acid composition ranging from 10 to 40 mol% was synthesized via nucleophilic step polymerization of 4,4′-dihydroxy-α-methylstilbene, 4,4′-dichloro-3,3′-disulfonic acid diphenylsulfone and 4,4′-dichlorodiphenylsulfone and blended with silica sol to form organic/inorganic nano-composite membranes. The organic/inorganic nano-composite copolymers produced show a high glass transition temperature and thermal decomposition temperatures from 318 to 451 °C. The copolymers present appropriate toughness during the membrane process. The equilibrium water uptake and proton conductivity of the obtained organic/inorganic nano-composite membranes were measured as functions of temperature, degree of sulfonation and silica content. In general, the water uptake increased from 8 to 37 wt.%, and the proton conductivity of the organic/inorganic nano-composite membranes increased from 0.003 to 0.110 S cm−1 as the degree of sulfonation increased from 10 to 40 mol%, the silica content increased from 3 to 10 wt.%, and the temperature increased from 30 to 80 °C. The single cell performance of the 40 mol% organic/inorganic nano-composite membrane with various silica contents ranged from 11 to 13 mW cm−2 at 80 °C, and the power density was higher than Nafion® 117. Including the thermal properties, swelling, conductivity and single cell performance, the nano-composite membranes are able to satisfy the requirements of proton exchange membranes for direct methanol fuel cells (DMFC).  相似文献   

5.
Proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Herein, sulfonated halloysite nanotubes (SHNTs) with tunable sulfonic acid group loading were synthesized and incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare nanocomposite membranes. Physicochemical characterization suggests that the well-dispersed SHNTs enhance the thermal and mechanical stabilities of nanocomposite membranes. The results of water uptake, ionic exchange capacity, and proton conductivity corroborate that the embedded SHNTs interconnect the ionic channels in SPEEK matrix and donate more continuous ionic networks. These networks then serve as proton pathways and allow efficient proton transfer with low resistance, affording enhanced proton conductivity. Particularly, incorporating 10% SHNTs affords the membrane a 61% increase in conductivity from 0.0152 to 0.0245 S cm−1. This study may provide new insights into the structure-properties relationships of nanotube-embedded conducting membranes for PEM fuel cell.  相似文献   

6.
Constructing consecutive proton-conducting nanochannels and optimizing nanophase-separation within proton exchange membrane (PEM) was of guiding significance for improving proton transfer. Metal organic framework (MOF), as a novel and functional material had drawn increasing attention in the research of proton PEM because of its flexible tunability and designability. Herein, a novel MOF-based nanofibrous mats (NFMs) were prepared by the self-assembly of zeolitic imidazole framework-67 (ZIF-67) onto polyacrylonitrile (PAN) NFMs. Subsequently, the ZIF-67 NFMs were incorporated into Nafion matrix to prepare ZIF-67@Nafion composite membrane which aimed at constructing consecutive proton-conducting channels. Especially, the acid–base pairs between N–H (ZIF-67 NFMs) and –SO3H (Nafion) could promote the protonation/deprotonation and subsequent proton leaping via Grotthuss mechanisms. As expected, the ZIF-67@Nafion-5 composite membrane showed a promising proton conductivity of 288 mS/cm at 80 °C and 100% RH, low methanol permeability of 7.98 × 10−7 cm2s−1, and superior power density of 298.68 mW/cm2 at 80 °C and 100% RH. In addition, the resulting composite membrane exhibited considerable enhancement in thermal stability and dimensional stability. This promising strategy provided a valuable reference for designing high-performance PEMs.  相似文献   

7.
A composite membrane composed of a sulfonated diblock copolymer (SDBC) based on poly(ether ether ketone) blocks copolymerized with partially fluorinated poly(arylene ether sulfone) and sulfonated carbon nanotubes (SCNTs) was fabricated by simple solution casting. Addition of the SCNT filler enhanced the water absorption and proton conductivity of membranes because of the increased per‐cluster volume of sulfonic acid groups, at the same time reinforced the membranes' thermal and mechanical properties. The SDBC/SCNT‐1.5 membrane exhibited the most improved physicochemical properties among all materials. It obtained a proton conductivity of 10.1 mS/cm at 120°C under 20% relative humidity (RH) which was 2.6 times more improved than the pristine membrane (3.9 mS/cm). Moreover, the single cell performance of the SDBC/SCNT‐1.5 membrane at 60°C and 60% RH at ambient pressure exhibited a peak power density of 171 mW/cm2 at a load current density of 378 mA/cm2, while the pristine membrane exhibited 119 mW/cm2 at a load current density of 294 mA/cm2. Overall, the composite membrane exhibited very promising characteristics to be used as polymer electrolyte membrane in fuel cells operated at intermediate RH.  相似文献   

8.
Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by 1H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H2/O2 single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm2 in comparison with Nafion® 112 (618.0 mW/cm2) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.  相似文献   

9.
Sulfonated poly(ether sulfone) (SPES) based proton exchange membranes (PEMs) are fabricated using sulfonated molybdenum disulfide (S-MoS2) nanosheets via facile solution casting method. SPES (DS = 30%) and S-MoS2 are synthesized and sulfonation is evidently observed in FTIR and XRD analysis. The anchoring of sulfonic acid group on exfoliated molybdenum disulfide (E-MoS2) and elemental composition of S-MoS2 are confirmed by XPS spectrum. Physico-chemical characteristics such as ion-exchange capacity (IEC), water uptake, swelling ratio and oxidation stability are found to be increases after the addition of S-MoS2 into SPES matrix. Increment in S-MoS2 content in SPES matrix decreases the surface contact angle due to the increase in hydrophilicity. Further, the dispersing ability of S-MoS2 in SPES matrix is evidently shown by an increase in surface roughness, tensile strength and thermal stability of the SPES/S-MoS2 nanocomposite membranes. On the whole, SPES/S-MoS2-1 membrane showed the highest proton conductivity of 5.98 × 10−3 Scm−1, selectivity of 19.6 × 104 Scm−3s, peak power density of 28.28 mWcm−2 and lesser methanol permeability of 3.05 × 10−8 cm2s−1. The strong interfacial interaction between SPES and S-MoS2 in nanocomposite membranes create strong hydrogen bond network to facilitate the proton conduction pathway via both vehicle and Grotthuss type mechanisms. Overall results suggested that the SPES/S-MoS2 nanocomposite membranes are superior and appropriate alternative for commercially high-cost Nafion® membranes for use in renewable direct methanol fuel cell (DMFC) devices.  相似文献   

10.
In this study, the side-chain type hybrid proton exchange membranes which based on metal-organic frameworks (MOFs) and organic matrix of sulfonated poly (arylene ether ketone sulfone) containing both long and short sulfonic acid side chains (S-C-SPAEKS) were prepared. MOF-801 was used as a template and then imidazole was encapsulated into MOF-801 as additional proton carriers. In imidazole -MOF-801, imidazole was used as a functional group to coordinate with the zirconium metal site of the functional group. Imidazole-MOF-801 and hybrid membranes were characterized by XRD, 1H NMR and FT-IR. These hybrid membranes exhibited excellent proton conductivities and good thermal stabilities. Compared to pure S-C-SPAEKS (0.0487 S cm?1 at 30 °C, 0.0809 S cm?1 at 80 °C), S-C-SPAEKS/0.5% Im-MOF-801 showed a great improvement (0.1205 S cm?1 at 30 °C, 0.1992 S cm?1 at 80 °C), which was about 2.5 times higher than that of pure S-C-SPAEKS and 2 times higher than that of commercial Nafion117 (0.1003 S cm?1 at 80 °C). The results indicated that imidazole functionalized MOFs and uneven side chain structure synergistically made an important contribution to proton transport. This series of hybrid membranes have the potential to be used as alternative proton exchange membranes.  相似文献   

11.
In this study, a three-dimensional, steady-state, non-isothermal numerical model of high temperature proton exchange membrane fuel cells (HT-PEMFCs) operating with novel sulfonated polybenzimidazole (SPBI) membranes is developed. The proton conductivity of the phosphoric acid doped SPBI membranes with different degrees of sulfonation is correlated based on experimental data. The predicted conductivity of SPBI membranes and cell performance agree reasonably with published experimental data. It is shown that a better cell performance is obtained for the SPBI membrane with a higher level of phosphoric acid doping. Higher operating temperature or pressure is also beneficial for the cell performance. Electrochemical reaction rates under the ribs of the bipolar plates are larger than the values under the flow channels, indicating the importance and dominance of the charge transport over the mass transport.  相似文献   

12.
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   

13.
Nanocomposite membranes of sulfonated polyether ether ketone (sPEEK) are prepared with polyaminobenzene sulfonic acid grafted single-walled carbon nanotubes copolymer (PABS-SWCNT) and its zwitterion interactions are studied. The nanocomposite membranes are prepared through solution cast technique using PABS-SWCNT as additive in different weight % (0.1, 0.15, and 0.2) ratio. The additive and nanocomposite membranes are characterized for its surface morphology, composition, thermal and physico-chemical properties. The nanocomposite membrane comprising optimized content of PABS-SWCNT (0.15 wt %) shows improved proton conductivity and reduced methanol crossover resulting in enhanced DMFC peak power density of 150 mW cm−2 in comparison to 110 mW cm−2 for sPEEK and 80 mW cm−2 for Nafion® 117 respectively. The improved durability till 100 h for sPEEK/PABS-SWCNT (0.15 wt %) compared to sPEEK and Nafion-117 confirms its viability in DMFC application.  相似文献   

14.
The cathode microporous layer (MPL) is fabricated by various multiwall carbon nanotubes (CNTs), and its influence on the performance of a proton exchange membrane fuel cell (PEMFC) is evaluated. Three types of CNT with different dimensions are employed in the experiments, and the conventional MPL made by acetylene black (AB) is also considered for the purpose of comparison. The results show that the employment of CNT as MPL composition indeed may improve fuel cell performance significantly in comparison with the case of AB. The type of CNT with the largest tube diameter and straight cylinder in shape exhibits the highest cell performance. The corresponding optimal CNT loading and polytetrafluoroethylene (PTFE) content in the MPL are also evaluated. Results show that the case of cathode MPL composed of 1.5 mg cm?2 CNT and 20 wt% PTFE exhibits the best performance in all the experimental cases. The present data reveal that the application of CNT for MPL fabrication is beneficial to promote PEMFC performance. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
Phosphoric acid-doped sulfonated poly(tetra phenyl isoquinoline ether sulfone)s (PA-SPTPIESs) were successfully synthesized for high temperature proton exchange membrane. Poly(tetra phenyl ether ketone sulfone)s (PTPEKS) were prepared from 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenyl benzene (BFBTPB) and bis(4-fluorohenyl) sulfone with bis(4-hydroxyphenyl) sulfone. The synthesis of the poly(tetra phenyl isoquinoline ether sulfone)s (PTPIESs), was carried out via an intramolecular ring-closure reaction of dibenzoylbenzene of PTPEKS with benzylamine. The sulfonated poly(tetra phenyl isoquinoline ether sulfone)s (SPTPIESs) were obtained by following sulfonation with concentrated sulfuric acid and doped by phosphoric acid. Different contents of sulfonated unit on PTPIESs (8, 12, 16 mol% of BFBTPB) and PA-SPTPIESs were studied by FT-IR, 1H NMR spectroscopy, and thermogravimetric analysis (TGA). Strong acid–base interaction effect between poly benzisoquinoline (PBI) and sulfonic acid groups formed ionic crosslinking network between polymer chains. The ion exchange capacity (IEC) and proton conductivity of PA-SPTPIESs were evaluated with degree of sulfonation and doping of phosphoric acid.  相似文献   

16.
Sulfonated poly(ether ether ketone) (SPEEK) membranes have been deposited on the both sides of a sulfonic acid functionalized graphene oxide (SGO) paper to form a proton exchange membrane (PEM) with a sandwiched structure. The obtained SPEEK/SGO/SPEEK membrane could exhibit proton conductivity close to Nafion® 112 and lower methanol permeability. The use of this SPEEK/SGO/SPEEK membrane greatly improves the performance of the semi-passive direct methanol fuel cell (DMFC). The semi-passive DMFC with the SPEEK/SGO/SPEEK membrane is found to be capable of delivering the peak power density 60% higher than that with the commercial Nafion® 112. This, along with its comparable durability to Nafion® 112, strongly suggests the great promise of using the SPEEK/SGO/SPEEK membrane as the PEM.  相似文献   

17.
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   

18.
In this work, composite membranes for a direct methanol fuel cell (DMFC) were prepared using a spraying method to improve cell performance especially at a high methanol concentration. Nafion polymer and mordenite as a filler were used for the composite membrane preparation using a spraying method and a conventional solution casting method and the membranes from the two methods were compared. SEM images showed that a more homogeneous composite membrane could be obtained using the spraying method. The effect of mordenite content was also studied. The membranes were consequently characterized and tested in DMFC operation. The results were compared to those prepared using the solution casting method at 30, 50, and 70 °C with methanol concentrations of 2, 4, and 8 M. It was found that the membrane with 5 wt.% mordenite from the spraying method showed a vast improvement in DMFC performance. When the cell was operated at 70 °C, the maximum power density of 5 wt.% mordenite from the spraying method was higher than that of commercial membrane and 5 wt.% from the solution casting method. Power densities from the 5 wt.% sprayed membrane were higher by around 29%, 40%, and 60% at 2, 4, and 8 M methanol concentration, respectively.  相似文献   

19.
In order to identify the best porous materials for the cryogenic physisorption of hydrogen, high-throughput calculations are performed starting, i.e., from the collected information in crystallographic databases. However, these calculations, like molecular simulations, require specific training and significant computational cost. Herein, a relatively simple procedure is proposed to estimate and compare hydrogen uptakes at 77 K and pressure values from 40 bar starting from the porous properties of MOF materials, without involving simulation tools. This procedure uses definitions for adsorption and considers the adsorbed phase as an incompressible fluid whose pressure-density change is that for the liquid phase at 19 K. For the 7000 structures from the CoRE MOF database, the average error of the predictions is only of 1% from reference values at 100 bar, with an SD of ±8%. This accuracy is lower than that from simulation tools, but involving lower computational cost and training.  相似文献   

20.
In the present study, TiO2 nanoparticles are used as inorganic nanofiller material to prepare nanocomposite proton exchange membrane (PEM). Sulfonated polyvinyl alcohol (SPVA) is synthesized by 4-formylbenzene-1,3-disulfonic acid disodium salt hydrate and water. The cross-linking reaction is performed by glutaraldehyde. These membranes were then dip coated with polyacrylic acid and chitosan alternately and one layer-by-layer (LBL), two LBL and three LBL membranes were prepared. The chemical structure evaluation of SPVA membrane is performed using FTIR. The direct methanol fuel cell (DMFC) catalysts of 10Cu/CeO2 and 10 Pt-10 CeO2/C were prepared by reduction reaction and hydrothermal technique. Thus obtained material was spin coated on 2 × 2 cm2 carbon paper to prepare catalyst anode/cathode. The morphology, size, and purity of catalyst particles are analysed by SEM, UV–visible spectroscopy, FTIR and EDS. Electrochemical analysis is also done to test the performance. Results show that Cu/CeO2 catalyst shows excellent catalysis towards methanol oxidation, which is better than 10 Pt-10 CeO2/C particles. The 10Cu/CeO2 catalyst gives peak voltage of 915 mV for infinite resistance, which is higher than the reported value of the conventional 20 Pt/C catalyst (810 mV).  相似文献   

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