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1.
Long-term operation of a polymer electrolyte membrane fuel cell (PEMFC) was carried out in constant-current (CC) and open-circuit-voltage (OCV) modes. The main factors causing electrocatalyst deactivation were found to be Pt sintering and dissolution. In Pt sintering, growth in particle size occurred mostly during the initial stage of operation (40 h). Pt dissolution occurred mostly at the cathode, rather than the anode, due to chemical oxidation of Pt to PtO by residual oxygen present in the cathode layer, resulting in a gradual decrease in cell performance during long-term operation. After the dissolution of PtO in water, Pt2+ was formed, which migrated from the cathode to the membrane phase, and was re-deposited as Pt crystal upon reduction by crossover hydrogen, as was confirmed by transmission electron microscopy (TEM) after long-term operation. Under normal operating conditions, there exists a balance at the cathode between chemical oxidation by oxygen and electrochemical reduction by input electrons. Therefore, Pt dissolution at the cathode is accelerated by an imbalance of these reactions under OCV conditions or by a high O2 concentration in the feed.  相似文献   

2.
A three‐dimensional and two‐phase numerical model is developed for a 25‐cm2 proton exchange membrane fuel cell (PEMFC) to investigate the effects of flow mode (coflow and counterflow) and relative humidity (anode 0%/100%; cathode 60%/100%) on the cell performance. Experimental studies are performed to validate this developed model. An equivalent membrane conductivity is proposed to describe the match level between current flux and membrane conductivity. It is found that the cell performance is enhanced under low relative humidity conditions because of the optimized equivalent membrane conductivity. More specifically, the voltage is improved from 0.611 to 0.637 V, and the equivalent membrane conductivity is enhanced from 10.35 to 11.11 S m?1 by replacing the coflow mode with counterflow mode at 1000 mA cm?2 when anode gas is dry and cathode gas is 100% hydrated. Both the anode and cathode relative humidities show an obvious influence on the PEMFC performance, and a suitable inlet humidity could ensure adequate hydration of membrane and avoid water flooding in gas diffusion layers simultaneously.  相似文献   

3.
Alkaline membrane (AM) shows fast transport of OH towards the anode, separates both electrodes, and prevents fuel cross-over. To achieve good membrane conductivity and performance, high concentration of positively charged groups (quaternary ammonium) is an essential requirement, which also leads excessive swelling and mechanical instability of the AMs. Further, directly grafted quaternary ammonium (QA) with main polymer chain substitution and/or elimination reactions under strong alkaline environment. To avoid above-mentioned problems, we report preparation of cross-linked chloromethylated polysulfone based AM using (4,4,-((3,3′-bis(chloromethyl)-[1.1′-biphenyl]-4,4-diyl)bis(oxy))dianiline) (BCBD), a multi-functional novel cross-linking agent. Reported strategy compensates 2 mol of chloromethyl groups consumed during cross-linking, but additional functional groups (4 mol) with cross-linking agent. These AMs are designed to avoid the nucleophilic substitution (SN2) (grafting quaternary ammonium (QA) groups at benzylic position), and Hofmann elimination (E2) reactions (unavailability of β-H), under strong alkaline environment. Effective cross-linking has been confirmed by spectral analysis, and improves membrane stabilities and fuel cell performance. Single-cell alkaline membrane fuel cell (AEMFC) performance of most suitable (CR-QPS-03) membrane, showed comparatively high performance (open circuit voltage (OCV): 0.813 V, maximum power density: 103.6 mW/cm2 at 260.0 mA/cm2) in compare with Nafion 117 membrane (OCV: 0.682 V, maximum power density: 63.36 mW/cm2 at 220.0 mA/cm2) under similar experimental conditions.  相似文献   

4.
Developing self-humidifying membrane electrode assembly (MEA) is of great significance for the practical use of proton exchange membrane fuel cell (PEMFC). In this work, a phosphoric acid (PA)-loaded Schiff base networks (SNW)-type covalent organic framework (COF) is proposed as the anode catalyst layer (CL) additive to enhance the PEMFC performance under low humidity conditions. The unique polymer structure and immobilized PA endow the proposed COF network with not only excellent water retention capacity but also proton transfer ability, thus leading to the superior low humidity performance of the PEMFC. The optimization of the additive content, the effect of relative humidity (RH) and PEMFC operating temperature are investigated by means of electrochemical characterization and single cell test. At a normal operation temperature of 60 °C and 38% RH, the MEA with optimized COF content (10 wt%) showes the maximum power density of 582 mW cm?2, which is almost 7 times higher than that of the routine MEA (85 mW cm?2). Furthermore, a preliminary durability test demonstrates the potential of the proposed PEMFC for practice operation under low humidity environment.  相似文献   

5.
Tantalum nitride (TaN) thin films are deposited on AISI 316L stainless steel by inductively coupled, plasma-assisted, reactive magnetron sputtering at various N2 flow rates. TaN film behavior is investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) conditions by using electrochemical measurement techniques for application as bipolar plates. The results of a potentio-dynamic polarization test under PEMFC cathodic and anodic conditions indicate that the corrosion current density of the TaNx films is of the order of 10−7 A cm−2 (at 0.6 V) and 10−8 A cm−2 (at −0.1 V), respectively; these results are considerably better than the individual results for metallic Ta films and AISI 316L stainless steel. The TaNx films exhibit superior stability in a potentio-static polarization test performed under PEMFC cathodic and anodic conditions. The interfacial contact resistance of the films is measured in the range of 50-150 N cm−2, and the lowest value is 11 mΩ cm2 at a compaction pressure of 150 N cm−2.  相似文献   

6.
A series of polyaniline nanofibers (PANFs) were synthesized and incorporated into gas diffusion electrodes (GDE) of proton exchange membrane fuel cells (PEMFC) to improve their performances at low relative humidity (RH) conditions. Three different placements to incorporate the PANFs in the anodes include (1) placing a PANFs layer between catalyst layer (CL) and membrane, (2) coating the CL with PANFs and catalyst mixed slurry, and (3) placing a PANFs layer between the CL and gas diffusion layer (GDL). Fuel cell performance data indicates that the last method is superior to the others and is adopted as incorporation method thereafter. Extensive studies on single cell performances have been conducted to compare the membrane electrode assemblies with and without the incorporation of PANFs in both anode and cathode. Polarization curves show the incorporation of H2SO4-doped PANFs is highly effective in improving the hydrophilic characteristic of the electrodes and thus can promote the PEMFC performance at low RH conditions. For example, with a lowering of reactant RH from 100 to 70%, the electrode with H2SO4-doped PANFs layer exhibits an increase in power density from 0.57 to 0.7 W cm−2. On the other hand, a traditional carbon-supported platinum electrode exhibits a decline of performance from 0.73 to 0.55 W cm−2.  相似文献   

7.
Aluminum alloy bipolar plates have unique application potential in proton exchange membrane fuel cell (PEMFC) due to the characteristics of lightweight and low cost. However, extreme susceptibility to corrosion in PEMFC operation condition limits the application. To promote the corrosion resistance of aluminum alloy bipolar plates, a Ni–P/TiNO coating was prepared by electroless plating and closed field unbalanced magnetron sputter ion plating (CFUMSIP) technology on the 6061 Al substrate. The research results show that Ni–P interlayer improves the deposition effect of TiNO outer layer and increase the content of TiN and TiOxNy phases. Compared to Ni–P and TiNO single-layer coatings, the Ni–P/TiNO coating samples exhibited the lowest current density value of (1.10 ± 0.02) × 10?6 A·cm?2 in simulated PEMFC cathode environment. Additionally, potential cyclic polarization measurements were carried out aiming to evaluate the durability of the aluminum alloy bipolar plate during the PEMFC start-up/shut-up process. The results illustrate that the Ni–P/TiNO coating samples exhibit excellent stability and corrosion resistance.  相似文献   

8.
A PdPt (10 wt% Pt) catalyst is used to replace platinum at the cathode of a proton exchange membrane fuel cell membrane electrode assembly (PEMFC MEA) whereas pure palladium is used as the anode catalyst. The catalysts are deposited on commercial carbon woven web and carbon paper GDLs by plasma sputtering. The relations between the depth density profiles, the electrode support and the fuel cell performances are discussed. It is shown that the catalyst gradient is an important parameter which can be controlled by the catalyst depth density profile and/or the choice of electrode support. An optimised electrode structure has been obtained, which allows limiting the platinum requirement. Under suitable conditions of a working PEMFC (80 °C and 3 bar absolute pressure), very high catalysts utilization is obtained at both electrodes, leading to 250 kW gPt−1 and 12.5 kW gPd−1 with a monocell fitted with a PdPt (10:1 weight ratio) cathode and a pure Pd anode.  相似文献   

9.
Corrosion performance of 316L stainless steel as a bipolar plate material in proton exchange membrane fuel cell (PEMFC) is studied under different simulated PEMFC anode conditions. Solutions of 1 × 10−5 M H2SO4 with a wide range of different F concentrations at 70 °C bubbled with hydrogen gas are used to simulate the PEMFC anode environments. Electrochemical methods, both potentiodynamic and potentiostatic, are employed to study the corrosion behavior. Scanning electron microscope (SEM) and atomic force microscope (AFM) are used to examine the surface morphology of the specimen after it is potentiostatic polarized in simulated PEMFC anode environments. X-ray photoelectron spectroscopy (XPS) analysis is used to identify the compositions and the depth profile of the passive film formed on the 316L stainless steel surface after it is polarized in simulated PEMFC anode environments. Mott–Schottky measurements are used to characterize the semiconductor passive films. The results of potentiostatic analyses show that corrosion currents increase with F concentrations. SEM examinations show that no localized corrosion occurs on the surface of 316L stainless steel and AFM measurement results indicate that the surface topography of 316L stainless steel becomes slightly rougher after polarized in solutions with higher concentration of F. From the results of XPS analysis and Mott–Schottky measurements, it is determined that the passive film formed on 316L stainless steel is a single layer n-type semiconductor.  相似文献   

10.
A high-level research is currently focused on the construction of polymer nanocomposite membranes with high proton conductivity (PC), peak power density (PD), and open circuit voltage (OCV) for polymer electrolyte membrane fuel cells (PEMFC) to substitute the commercial Nafion-211 membrane. The present study deals with the solvent-casting process for producing ZrO2 nanoparticles (1–7 wt %) dispersed on phosphoric acid (PA) doped polyethylene imine and polyvinyl alcohol (PA-PEI/PVA) polymer nanocomposites (PNCs). ZrO2 (5%) dispersed PA-PVA/PEI PNCs showed the highest ion-exchange capacity (IEC) of 2.94 mmol/g−1 at room temperature (RT), and PC of 4.34 10−2 S/cm−1 at 120 °C. Experiments on the PNCs were carried out at 120 °C to evaluate their performance and usability in medium-temperature polymer electrolyte membrane fuel cells (MT-PEMFCs). The results indicate a practical and effective route for the fabrication of a composite membrane that has a semi-interpenetration network structure with abundant active protonated groups, and has future prospects and widespread application in MT-PEMFCs.  相似文献   

11.
Membrane electrode assemblies with Nafion/nanosize titanium silicon dioxide (TiSiO4) composite membranes were manufactured with a novel ultrasonic-spray technique and tested in proton exchange membrane fuel cell (PEMFC). Nafion/TiO2 and Nafion/SiO2 nanocomposite membranes were also fabricated by the same technique and their characteristics and performances in PEMFC were compared with Nafion/TiSiO4 mixed oxide membrane. The composite membranes have been characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, water uptake, and proton conductivity. The composite membranes gained good thermal resistance with insertion of inorganic oxides. Uniform and homogeneous distribution of inorganic oxides enhanced crystalline character of these membranes. Gas diffusion electrodes (GDE) were fabricated by Ultrasonic Coating Technique. Catalyst loading was 0.4 mg Pt/cm2 for both anode and cathode sides. Fuel cell performances of Nafion/TiSiO4 composite membrane were better than that of other membranes. The power density obtained at 0.5 V at 75 °C was 0.456 W cm−2, 0.547 W cm−2, 0.477 W cm−2 and 0.803 W cm−2 for Nafion, Nafion/TiO2, Nafion/SiO2, and Nafion/TiSiO4 composite membranes, respectively.  相似文献   

12.
A poly(R1R2R3)–N+/H3PO4 composite membrane has been developed for use in a polymer electrolyte fuel cell (PEMFC). The quaternized polysulfone (QNPSU) membrane doped with H3PO4 showed high proton conductivity (0.12 S cm−1) at 160 °C and gave good performance in a single fuel cell tests. The peak power density with the QNPSU/H3PO4 composite membrane (at 150 °C, with dry H2/O2) was greater than 0.7 W cm−2. The effect of the phosphoric acid doping level on fuel cell performances with the QNPSU membrane was investigated. The data show that the QNPSU/H3PO4 composite membrane is promising for higher temperature PEMFC applications. The study demonstrated that the poly(R1R2R3)–N+/H3PO4 composite system produced an effective method to connect phosphoric acid to a non-conducting polymer structure, to produce a promising membrane for phosphoric acid polymer electrolyte membrane fuel cells.  相似文献   

13.
In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H2, N2, and CO2 were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H2 permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H2 permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H2 permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H2 and 25% N2, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H2 permeation flux was 0.185 mol s?1 m?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H2 permeation flux.  相似文献   

14.
Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd50Pt50, Pd75Pt25, Pd90Pt10 and Pd95Pt5, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd95Pt5/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd95Pt5/C was as low as 0.02 mg cm−2, the specific power (power to mass of Pt in the MEA) of Pd95Pt5/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd50Pt50/C and Pd75Pt25/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.  相似文献   

15.
A mixed metal oxide-coated Ti felt was constructed for use as a porous transport layer (PTL) in a proton exchange membrane (PEM) water electrolyzer. The PTL was fabricated by coating Ti felt with 0.43 mgTaOx cm?2 and 1 mgIr + Ru cm?2 IrO2–RuO2-TaOx using a thermal decomposition method. The coated Ti felts exhibited high conductivity, mass transport performance, stability and oxygen evolution reaction (OER) catalytic activities. The stability of IrO2–RuO2-TaOx coating obviously improved than traditional electroplated Pt coating. Using the PTL, a single cell performance of 1.836 V @ 2000 mA cm?2 was achieved at 80 °C under ambient pressure with 1 mg cm?2 of precious metal in anode CL. However, the precious metal loading is about 2 mg cm?2 in common PEM electrolyzer anode catalyst layer (CL). The IrO2–RuO2-TaOx-coated Ti felt proved to be a promising low-cost PTL for PEM water electrolysis with high performance.  相似文献   

16.
This study examines the effect of hydrogen peroxide (H2O2) on the open-circuit voltage (OCV) of a proton exchange membrane fuel cell (PEMFC) and the reduction of H2O2 in the membrane using a ruthenium/carbon catalyst (Ru/C) at the anode. Each cathode and anode potential of the PEMFC in the presence of H2O2 is examined by constructing a half-cell using 1.0 M H2SO4 solution as an electrolyte and Ag/AgCl as the reference electrode. H2O2 is added to the H2SO4 solution and the half-cell potential is measured at each H2O2 concentration. The cathode potential is affected by the H2O2 concentration while the anode potential remains stable. A Ru catalyst is used to reduce the level of H2O2 formation through O2 cross-over at the interface of a membrane and the anode. The Ru catalyst is known to produce less H2O2 through oxygen reduction at the anode of PEMFC than a Pt catalyst. A Ru/C layer is placed between the Nafion® 112 membrane and anode catalyst layer and the cell voltage under open-circuit condition is measured. A single cell is constructed to compare the OCV of the Pt/C only anode with that of the Ru/C-layered anode. The level of hydrogen cross-over and the OCV are determined after operation at a current density of 1 A cm−2 for 10 h and stabilization at open-circuit for 1 h to obtain an equilibrium state in the cell. Although there is an increase in the OCV of the cell with the Ru/C layer at the anode, excessive addition of Ru/C has an adverse effect on cell performance.  相似文献   

17.
Aliphatic alcohol mainly, ethanol, methanol and their mixture were subjected to electrooxidation study using cyclic voltammetry (CV) technique in a three electrodes half cell assembly (PGSTAT204, Autolab Netherlands). A single cell set up of direct alcohol alkaline fuel cell (DAAFC) was fabricated using laboratory synthesized alkaline membrane to validate the CV results. The DAAFC conditions were kept similar as that of CV experiments. The anode and cathode electrocatalysts were Pt-Ru (30%:15% by wt.)/Carbon black (C) (Alfa Aesar, USA) and Pt (40% by wt.)/High Surface Area Carbon (CHSA) (Alfa Aesar, USA) respectively. The CV and single cell experiments were performed at a temperature of 30 °C. The anode electrocatalyst was in the range of 0.5 mg/cm2 to 1.5 mg/cm2 for half cell CV analysis. The cell voltage and current density data were recorded for different concentrations of fuel (ethanol or methanol) and their mixture mixed with different concentration of KOH as electrolyte. The optimum electrocatalyst loading in half cell study was found to be 1 mg/cm2 of Pt-Ru/C irrespective of fuel used. The single cell was tested using optimum anode loading of 1 mg/cm2 of Pt-Ru/C which was found in CV experiment. Cathode loading was kept similar, in the order of 1 mg/cm2 Pt/CHSA. In single cell experiment, the maximum open circuit voltage (OCV) of 0.75 V and power density of 3.57 mW/cm2 at a current density of 17.76 mA/cm2 were obtained for the fuel of 2 M ethanol mixed with 1 M KOH. Whereas, maximum OCV of 0.62 V and power density of 7.10 mW/cm2 at a current density of 23.53 mA/cm2 were obtained for the fuel of 3 M methanol mixed with 6 M KOH. The mixture of methanol and ethanol (1:3) mixed with 0.5 M KOH produced the maximum OCV of 0.66 V and power density of 1.98 mW/cm2 at a current density of 11.54 mA/cm2.  相似文献   

18.
This study demonstrates the successful development of hybrid mesoporous siliceous phosphotungstic acid (mPTA-Si) and sulfonated poly ether ether ketone (SPEEK) as a proton exchange membrane with a high performance in hydrogen proton exchange membrane fuel cells (PEMFC). SPEEK acts as a polymeric membrane matrix and mPTA-Si acts as the mechanical reinforcer and proton conducting enhancer. Interestingly, incorporating mPTA-Si did not affect the morphological aspect of SPEEK as dense membrane upon loading the amount of mPTA-Si up to 2.5 wt%. The water uptake reduced to 14% from 21.5% when mPTA-Si content increases from 0.5 to 2.5 wt% respectively. Meanwhile, the proton conductivity increased to 0.01 Scm?1 with 1.0 wt% mPTA-Si and maximum power density of 180.87 mWcm?2 which is 200% improvement as compared to pristine SPEEK membrane. The systematic study of hybrid SP-mPTA-Si membrane proved a substantial enhancement in the performance together with further improvement on physicochemical properties of parent SPEEK membrane desirable for the PEMFC application.  相似文献   

19.
An innovative small-scale cogeneration system based on membrane reformer and PEM fuel cells is under development within the FluidCELL project. An experimental campaign has been carried out to characterize the PEM fuel cell and to define the operative conditions when integrated within the system. The hydrogen feeding the PEM is produced by a membrane reactor which in principle can separate pure hydrogen; however, in general, hydrogen purity is around 99.9%–99.99%. The focus of this work is the assessment of the PEM performance under different hydrogen purities featuring actual membrane selectivity and gases build-up by anode off-gas recirculation. Their effects on the cells voltage and local current distribution are measured at different conditions (pressure, humidity, stoichiometry, with and without air bleeding, in flow-through and dead-end operation). In flow-through mode, the cell voltage is relatively insensitive to the presence of inert gases (e.g. ?20 mV with inerts/H2 from 0 to 20·10?2 at 0.3 A/cm2), and resistant also to CO (e.g. ?35 mV with inerts/H2 = 20·10?2 and CO/H2 from 0 to 20·10?6 at 0.3 A/cm2), thanks to the Ru presence in the anode catalyst. Looking at the current density distribution on the cell surface, the most critical areas are the cathode inlet, likely due to insufficient air humidification, and the anode outlet, because of low hydrogen concentration and CO poisoning of the catalyst. Dead-end operation is also investigated using humid or impure hydrogen. In this case relatively small amount of impurities in the hydrogen feed rapidly reduces the cell voltage, requiring frequent purges (e.g. every 30 s with inerts/H2 = 0.5·10?2 at 0.3 A/cm2). These experiments set the basis for the management of the PEMFC stack integrated into the m-CHP system based on the FluidCELL concept.  相似文献   

20.
The thermal contact resistance (TCR) is the main component of proton exchange membrane fuel cell (PEMFC) thermal resistance due to the existence of surface roughness between the components of PEMFC, and the influence of TCR is often ignored in traditional three dimensional PEMFC simulations. In this paper, the heat and mass transfer characteristics including polarization curve, power density curve, temperature distribution, membrane water content distribution, membrane current density are studied under different component surface roughness conditions, and finally the effect of each TCR on the PEMFC performance is studied. It is found that under the same operating conditions, the TCR makes the radial heat transfer of the PEMFC decrease, and the temperature of the membrane electrode and the temperature difference of each component of the PEMFC is higher than that of the model without TCR. When the surface roughness of components in the PEMFC equals 1 μm, 2 μm, 3 μm, the cell current density decreases by 6.56%, 12.46% and 17.17% respectively when the output cell voltage equals 0.3 V, and the cell power density decreases by 3.64%, 7.54%, 13.14% respectively when the cell current density equals 1.2 A·cm?2. When the TCR between the CL and PEM equals 0.003 K·m2·W?1, 0.005 K·m2·W?1, 0.01 K·m2·W?1, the cell current density is increased by 2.30%, 3.65%, 6.74% respectively under the condition that the output cell voltage equals 0.3 V, and the cell power density is increased by 1.24%, 1.85%, 3.10% respectively when the cell current density equals 1.2 A·cm?2. The results show that the numerical simulation of PEMFC cannot ignore the effect of TCR.  相似文献   

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