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1.
A proton exchange membrane fuel cell operating with no external humidification support was successfully reported using a novel silica composite layer on the anode side (Pt/C/SiO2/Nafion). The nanosilica derived from tetramethoxy silane (TMOS) provided excellent porous morphology to retain water and hydrate protons. This layer provides a well-humidified environment for protons and easy proton transfer from the catalyst surface to the membrane electrolyte. The characteristics of the silica composite layer were investigated by various characterization methods: SEM, XRD, TEM, XPS, EIS, and TGA. A single cell fabricated with the anode containing this new silica composite layer showed a performance of 0.9 W/cm2 which is two folds greater when tested with the commercial catalyst MEA (0.45 W/cm2). MEA delivered a constant output power (at 0.6 V) under dry and humidified gas conditions which shows excellent electrochemical stability and durability.  相似文献   

2.
Phosphoric acid used as a proton-conductive medium in high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) poisons the Pt surface and prevents oxygen transport in the cathode catalyst layer. The hydrophobic binders in the catalyst not only maintain the catalyst layer structure but also control the phosphoric acid distribution. In this study, polytetrafluoroethylene (PTFE)/carbon black (Vulcan XC-72R) added to the catalyst layer generates an oxygen transport channel. The catalyst layers coated on the gas diffusion layer by the bar-coating method serve as the cathode. High PTFE content causes hydrophobicity in the catalyst layer. The membrane electrode assembly (MEA) with 6 wt% PTFE/Vulcan results in the highest peak power density (0.347 W cm−2) and voltage (0.653 V) at 0.2 A cm−2. A critical reason for its high performance is having the lowest Rct + Rmt values measured at 0.6 V and 0.4 V. These results could contribute to improving the MEA performance for HT-PEMFCs.  相似文献   

3.
The conventional electrodes of direct methanol fuel cells (DMFCs) usually encounter a problem that the catalysts sink into the diffusion layer after a period of operation, causing a lowered catalyst utilization and degraded cell performance. Aiming to alleviate this problem, in this work a novel anode electrode structure is proposed, in which a microporous layer containing Nafion polymer is added between the catalyst layer and the microporous layer with PTFE. The presence of the Nafion-contained layer can expand the three-phase interface region of the electrochemical reactions and improve the utilization of the catalyst. The single cell test showed that the peak power densities of the novel membrane electrode assembly (MEA) fed with 0.5 M and 2 M methanol solutions reached 38.35 mW cm−2 and 101.82 mW cm−2, which increased by 100.42% and 15.27% compared with those of conventional single microporous layer. Electrochemical impedance spectroscopy (EIS) measurements indicated the charge transfer resistance of the conventional MEA structure was increased by 303.78%, while the new one was decreased by 47.91% after continuously operating for 48 h. The anode electrochemical active surface area (ECSA) values of the novel MEA and the conventional MEA were 52.6 m2 g-1 and 44.3 m2 g-1. These experimental results showed that the performance of the double microporous layer MEA was higher than that of the conventional MEA. This new microporous layer structure is promising to be used in fuel cells to improve cell performance and alleviate performance degradation after long-term operating.  相似文献   

4.
High cost and poor durability of Pt-based cathode catalysts for oxygen reduction reaction (ORR) severely hamper the popularization of proton exchange membrane fuel cells (PEMFCs). Tailoring carbon support is one of effective strategies for improving the performance of Pt-based catalysts. Herein, petroleum vacuum residue was used as carbon source, and nitrogen-doped porous carbon (N-PPC) was synthesized using a simple template-assisted and secondary calcination method. Small Pt nanoparticles (Pt NPs) with an average particles size of 1.8 nm were in-situ prepared and spread evenly on the N-PPC. Interestingly, the lattice compression (1.08%) of Pt NPs on the N-PPC (Pt/N-PPC) was clearly observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), which was also verified by the shift of (111) crystal plane of Pt on N-PPC to higher angles. The X-ray photoelectron spectroscopy (XPS) results suggest that the N-PPC support had a strong effect on anchoring Pt NPs and endowing surface Pt NPs with lowered d band center. Thus, the Pt/N-PPC as a catalyst simultaneously boosted the ORR activity and durability. The specific activity (SA) and mass activity (MA) of the Pt/N-PPC at 0.9 V reached 0.83 mA cm−2 and 0.37 A mgPt−1, respectively, much higher than those of the commercial Pt/C (0.21 mA cm−2 and 0.11 A mgPt−1) in 0.1 M HClO4. The half-wave potential (E1/2) of Pt/N-PPC exhibited only a minimal negative shift of 7 mV after 30,000 accelerated durability tests (ADT) cycles. More importantly, an H2–O2 fuel cell with a Pt/N-PPC cathode achieved a power density of 866 mW cm−2, demonstrating that the prepared catalyst has a promising application potential in working environment of PEMFCs.  相似文献   

5.
Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO2) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm2 when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm2. Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.  相似文献   

6.
This study presents a novel and highly efficient CeO2-based type of additives to improve the performance of PEM fuel cells. Cerium(IV) oxide (CeO2) nanorods and CeO2 nanorod decorated nitrogen-doped reduced graphene oxide (NrGO) (CeO2/NrGO) were synthesized and utilized to enhance the ORR performance of PEMFCs. With a low energy transition between Ce+3 to Ce+4 and its high catalytic activity, CeO2 could promote O2 reduction. The structural properties of CeO2 nanorods and the CeO2/NrGO composite were investigated using XRD, RAMAN, SEM, TEM, TGA, BET, and XPS. The synthesized CeO2 nanorods and CeO2/NrGO composite were mixed with a low platinum loading (0.09 mgPt.cm−1), and ex-situ electrochemical characterizations were performed (CV and LSV) to evaluate their catalytic activities. Fuel cell performance tests and in-situ impedance analyses were also conducted to confirm the electrochemical results. Compared to commercial Pt/C-based MEA (269 mW.cm−2), the addition of both CeO2 nanorods (382 mW.cm−2) and CeO2/NrGO (389 mW.cm−2) to the catalyst layer showed a significant enhancement in fuel cell performance, due to the unique oxygen buffer ability of the synthesized additives.  相似文献   

7.
Rhodium with activated carbon as carbon base layer (Rh/AC) was exploited as an oxygen reduction reaction (ORR) catalyst to explore its applicability in microbial fuel cell (MFC). Four MFCs were fabricated using the Rh/AC catalyst, adopting varying Rh loadings of 0.5, 1.0 and 2.0 mg cm−2 and without Rh on carbon felt cathode in order to understand the optimum loading of this catalyst to enhance the performance of MFC. The participation of Rh/AC in ORR was confirmed by cyclic voltammetry and electron impedance spectroscopy analysis, which supported the enhanced charge transfer capacity of the cathode modified with the prepared catalysts. Volumetric power density of MFC was found to be improved by 2.6 times when Rh/AC was used as cathode catalyst (9.36 W m−3) at a loading of 2.0 mg cm−2 in comparison to the control MFC (3.65 W m−3) without Rh on the cathode. It was thus inferred that the increase in the Rh loading up to 2 mg cm−2 can improve the performance of MFC significantly.  相似文献   

8.
Polybenzimidazole (PBI) was studied as an ionomer binder at varying ratios (1–7) in a 20–40 wt% Pt–Pd/C cathode-coupled catalyst layer for the oxygen reduction reaction (ORR) in a high-temperature proton exchange membrane fuel cell (HT-PEMFC). Catalytic activity was examined by CV and LSV, while the properties of the catalysts were characterized by FESEM-EDX, N2 adsorption–desorption, XRD and FTIR. The results showed that the distribution of metals on the carbon surface, carbon wall thickness and the interaction between ionomer and coupled catalysts affected the ORR performance. The fabricated membrane electrode assembly with 5:95 PBI: 30 wt% Pt–Pd/C catalyst ratio exhibited the best performance and highest durability for HT-PEMFC at 170 °C, yielding a power density of 1.30 Wcm−2 with 0.02 mgPt/cm Pt loading. This performance of ultra-low metal loading of coupled Pt–Pd/C electrocatalyst with PBI binder was comparable to those reported by other studies, highlighting a promising catalyst for fuel cell application.  相似文献   

9.
To improve the utilization of platinum and reduce the manufacturing cost of proton exchange membrane fuel cell (PEMFC), the electrostatic spraying was used to prepare the cathode catalyst layer of membrane electrode assembly (MEA) with platinum loading varying from 0.1 to 0.01 mg cm?2. The performance of fuel cell was tested and analyzed by electrochemical impedance and polarization curve. Our results show that the platinum carbon (Pt/C) particles deposited by electrostatic spraying were well dispersed and the microporous structure of catalyst layer (CL) were relatively uniform. Replacing the CCS type MEA (catalyst coated on gas diffusion layer substrate) with the CCM type MEA (catalyst coated on proton exchange membrane) can reduce its electrochemical impedance and improve the power density of fuel cell. Compared to the Pt/C catalyst with a platinum mass fraction of 60%, a lower platinum-carbon ratio catalyst is more conducive to the uniform dispersion of catalyst particles and efficient utilization of platinum in the preparation of MEA with ultra-low platinum loading. However, their difference in peak power density decreases with the increase of platinum loading. Besides, increasing the back pressure can improve the performance of fuel cell, when the back pressure increased to 0.15 Mpa and the feeding gases were set as H2/O2, the peak power density of 0.56 W cm?2 was obtained by the MEA with cathode platinum loading of 0.01 mg cm?2, which is corresponding to the cathode platinum utilization of 56 kW·gPt?1cathode.  相似文献   

10.
In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm2 and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm-2 at 0.6 V and 1600 mAcm−2 under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.  相似文献   

11.
Transition metal phosphides represent a class of promising electrocatalysts for electrochemical water oxidization and other energy conversion reactions. In this work, we report a novel seal strategy, followed by a second step phosphorization treatment, produces Ni-Fe-P heterostructure directly grown on nickel foam that shows highly catalytic activity for electrochemical water oxidation. The as-prepared catalyst exhibits an excellent electrocatalytic activity, manifested by a current density of 20 mA cm−2 with a very low overpotential (260 mV) for oxygen evolution reaction along with an extremely small Tafel slope of 27 mV decade−1 and a very excellent durability of 120 h in alkaline solution. The excellent performance with exceptional durability owe much to the synergistic effect between the Ni-Fe-P heterostructure and the outer oxidized layer. Remarkably, a current density of 10 mA cm−2 was reached at a low cell voltage of 1.63 V when the original electrode and surface oxidized electrode are used as cathode and anode, respectively.  相似文献   

12.
A polytetraphenylporphyrin iron (II) (PTPPFe) oxygen reduction reaction (ORR) catalyst for aluminum-air fuel cells (AAFCs) is prepared. Thermogravimetric analysis results show that PTPPFe is stable at temperatures below 600 °C. X-ray photoelectron spectroscopy reveals that the active site of PTPPFe/C is Fe–N4 in the porphyrin ring. Rotating disk electrode measurements in 1 mol L−1 NaOH solution demonstrate that the initial potential for ORR is 0.142 V vs. Hg/HgO/OH (1 mol L−1 KOH, 0.098 V vs. NHE) at 20 °C, and that ORR mainly occurs through a four-electron process. The half-wave potentials for PTPPFe/C and the Pt/C catalyst are 0.071 and 0.079 V, respectively. Almost no performance degradation is observed over continuous cyclic voltammetry at 10 000 cycles, linear sweep voltammetry at 200 cycles, and 60 h of chronoamperometry test. After durability tests, the ultraviolet–visible spectrum of PTPPFe does not change from the initial characteristics. The discharge performance of AAFC has a power density of 47.5 mW cm−2 at 20 °C in 6 mol L−1 NaOH electrolyte solution. During continuous discharge for 10 h, the potential of AAFC decreases by less than 0.01 V at 40 mA cm−2.  相似文献   

13.
Designing oxygen reduction reaction (ORR) catalysts with high activity and long durability is significant for the development of proton exchange membrane fuel cells. Herein, the optimized platinum nanowires are used as templates for inducing growth of cobalt-containing metal-organic framework, deriving uniform nanofibers. After the calcination, the metal ions are transferred into the nitrogen-rich porous carbon, and wrapped by the carbon skeleton to form the PtCo bimetal incorporated nanofibers as high-performance ORR electrocatalyst. The Pt4Co@NC-900 catalyst yields high specific activity (1.37 mA cm−2) in comparison to Pt/C (0.38 mA cm−2). The mass activity (MA) of Pt4Co@NC-900 catalyst is approximately 3.8-fold higher than that of the commercial Pt/C under acidic conditions. After the accelerated durability tests, the Pt4Co@NC-900 catalyst presents only 16% loss in MA, while Pt/C catalyst retains 73.0% of the initial MA. The improved ORR performance can be ascribed to the synergistic interaction between Co and Pt.  相似文献   

14.
The purpose of this study is to develop a novel binary Iridium-Cobalt/C catalyst as a suitable substitute for platinum/C applied in proton exchange membrane fuel cells (PEMFCs). The carbon-supported IrCo catalysts were successfully synthesized using IrCl3 and C4H6CoO4 as the Ir and Co precursors respectively, in ethylene glycol (EG) refluxing at 120 °C. The nanostructured catalysts were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscope (TEM). Homogeneous catalyst particles supported on carbon showed a size of proximately 2 nm. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were conducted for the characterization of the catalyst performances. With a cathodic loading of 0.4 mgIr cm−2, 20%Ir-30%Co/C achieved a maximum power density of 501.6 mW cm−2 at 0.418 V, with a 50 cm2 H2/O2 single cell. Although such a performance is about 26% lower than commercial Pt/C catalyst, it is still helpful in terms of Pt replacement and cost reduction.  相似文献   

15.
Factors as the Pt/C ratio of the catalyst, the binder content of the electrode and the catalyst deposition method were studied within the scope of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The Pt/C ratio of the catalyst allowed to tune the thickness of the catalytic layer and so to minimize the detrimental effect of the phosphoric acid flooding. A membrane electrode assembly (MEA) with 0.05 mgPtcm−2 at anode and 0.1 mgPtcm−2 at cathode (0.150 mgPtcm−2 in total) attained a peak power density of 346 mW cm−2. It was proven that including a binder in the catalytic layer of ultra-low Pt loading electrodes lowers its performance. Electrospraying-based MEAs with ultra-low Pt loaded electrodes (0.1 mgPtcm−2) rendered the best (peak power density of 400 mW cm−2) compared to conventional methods (spraying or ultrasonic spraying) but with the penalty of a low catalyst deposition rate.  相似文献   

16.
Increasing worldwide energy consumption has prompted considerable study into energy generation and energy storage systems in recent years. Chemical fuels may be produced efficiently via electrocatalytic water splitting, which uses electric and solar power. The development of efficient anodic electrocatalysts for efficient oxygen evolution reaction (OER) is a greater concern of present energy research. Cerium oxide (CeO2) are promising electrocatalysts that exhibit outstanding OER but their reduced stability obstructs the practical application. A novel strategy was established to construct an effective catalyst of heteroatom (N, B, P and S) doped CeO2 matrix were prepared. Moreover, the doping of heteroatoms into the CeO2 matrix processes the improved electronic conductivity, reactive sites, increases the electrochemical catalytic activity, which enhances the water oxidation reaction. Consequently, well-suited alkaline electrolysers were brought together for water oxidation to ideal OER electrocatalytic activity. The OER activity of the electrocatalysts follows the order of S–CeO2 (190 mV@10 mA cm−2), N– CeO2 (220 mV @10 mA cm−2), P– CeO2 (230 mV @10 mA cm−2), B–CeO2 (250 mV @10 mA cm−2) and CeO2 (260 mV @10 mA cm−2) in 1 M of KOH. From the kinetics analysis, Tafel slope value achieved for catalysts CeO2, B–CeO2, P–CeO2, N–CeO2 and S–CeO2 are 142 mV dec−1,121 mV dec−1, 102 mV dec−1, 98 mV dec−1 and 83 mV dec−1 respectively. These results validate that the S–CeO2 electrode is prominent for OER performance with the requirement of cell voltage of 1.42 V at 10 mA cm−2 current density. In addition, sulphur doped CeO2 relatively have excellent stability through chrono-potentiometric analysis lasting for 20 h. Although the heteroatoms doped CeO2 is acts as anode material, the preparation method is widespread, which will reduce the synthesis cost and streamline the preparation of electrode for OER. This research effort delivers a complete advantage for the development of robust, environmentally friendly and highly dynamic electrocatalysts for OER activity.  相似文献   

17.
Oxygen evolution reaction (OER) is regarded as a limit-efficiency process in electrochemical water splitting generally, which needs to develop the effective and low-cost non-noble metal electrocatalysts. Oxygen vacancies have been verified to be beneficial to enhance the electrocatalytic performance of catalysts. Herein, we report the facile synthesis of reduced CoFe2O4/graphene (r-CFO/rGO) composite with rich oxygen vacancies by a citric acid assisted sol-gel method, heat treatment process and the sodium borohydride (NaBH4) reduction. The introduction of graphene and freezing dry technique prevents the restacking of GO and the aggregation of CFO nanoparticles (NPs) and increases the electronic conductivity of the catalyst. Fast heating rate and low anneal temperature favors to obtain low crystallinity and lattice defects for CFO. NaBH4 reduction treatment further creates the rich oxygen vacancies and electrocatalytic active sites. The obtained r-CFO/rGO with high specific surface area (108 m2 g−1), low crystallinity and rich oxygen vacancies demonstrates a superior electrocatalytic activity with the smaller Tafel slope (68 mV dec−1), lower overpotential (300 mV) at the current density of 10 mA cm−2, and higher durability compared with the commercial RuO2 catalyst. This green, low-cost method can be extended to fabricate similar composites with rich defects for wide applications.  相似文献   

18.
An ultra-low-platinum catalyst based on finely dispersed platinum (Pt) deposited on a highly porous complex microporous layer was investigated as a candidate of durable anode catalyst for hydrogen oxidation reaction (HOR) in proton exchange membrane fuel cells. Etching of teflonated and nitridized base carbon substrate in oxygen plasma and simultaneous deposition of cerium oxide were applied to increase active surface area and electrochemical activity of the platinum nanocatalyst. Ultra-low loadings of Pt (between 0.85 and 8.5 μg cm−2) deposited by magnetron sputtering on this substrate were assembled with Nafion 212 membrane and commercially available Pt/C cathodes (300-400 μg cm−2 Pt). Such membrane electrode assembly (MEA) with extremely low Pt content at anode can deliver high output power densities, reaching 0.95 W cm−2 or 0.65 W cm−2 with only 1.7 μg cm−2 of Pt, using H2 as fuel and pure O2 or air as an oxidant, respectively. Although electrocatalysts with highly dispersed active metals are known to often suffer from irreversible degradation, the above MEAs proved to be very stable when the cell was subjected to a durability test under heavy duty conditions of on/off cycling. The system with lower Pt content is more prone to water flooding which can, however, be eliminated by maintaining better control over the fuel humidity. Average decay of the cell voltage less than 50 μV h−1 was obtained in the cycling regime, while excellent stability <10 μV h−1 is achievable under the static load of 0.4 A cm−2.  相似文献   

19.
Searching for efficient, stable and low-cost nonprecious catalysts for oxygen and hydrogen evolution reactions (OER and HER) is highly desired in overall water splitting (OWS). Herein, presented is a nickel foam (NF)-supported MoS2/NiFeS2 heterostructure, as an efficient electrocatalyst for OER, HER and OWS. The MoS2/NiFeS2/NF catalyst achieves a 500 mA cm−2 current density at a small overpotential of 303 mV for OER, and 228 mV for HER. Assembled as an electrolyzer for OWS, such a MoS2/NiFeS2/NF heterostructure catalyst shows a quite low cell voltage (≈1.79 V) at 500 mA cm−2, which is among the best values of current non-noble metal electrocatalysts. Even at the extremely large current density of 1000 mA cm−2, the MoS2/NiFeS2/NF catalyst presents low overpotentials of 314 and 253 mV for OER and HER, respectively. Furthermore, MoS2/NiFeS2/NF shows a ceaseless durability over 25 h with almost no change in the cell voltage. The superior catalytic activity and stability at large current densities (>500 mA cm−2) far exceed the benchmark RuO2 and Pt/C catalysts. This work sheds a new light on the development of highly active and stable nonprecious electrocatalysts for industrial water electrolysis.  相似文献   

20.
Low-temperature operation of solid oxide fuel cells (SOFCs) results in deterioration in electrochemical performance due to sluggish oxygen reduction reaction (ORR) at the cathode. To enhance the reaction pathway for ORR, La0.8Sr0.2MnO3 (LSM) nanofibers were fabricated by electrospinning and used for low-temperature solid oxide fuel cells operated at 600–700 °C. The morphological and structural characteristics show that the electrospun LSM nanofiber has a highly crystallized perovskite structure with a uniform elemental distribution. The average diameter of the LSM nanofiber after sintering is 380 nm. A symmetric cell of nanofiber-based LSM cathode on scandia-stabilized zirconia (SSZ) electrolyte pellet exhibits much lower area specific resistances compared to commercial LSM powder-based cathode. A single cell based on the nanofiber LSM cathode on yttrium-doped barium cerate-zirconia (BCZY) electrolyte exhibits a power density of 0.35 Wcm−2 at 600 °C, which increases to 0.85 Wcm−2 at 700 °C. The cell has an area specific resistance (ASR) of 0.46 Ωcm2 at 600 °C, which decreases to 0.07 Ωcm2 at 700 °C. The results indicate that the LSM electrode fabricated by the electrospinning process produces a nanostructured porous electrode which optimizes the microstructure and significantly enhances the ORR at the cathode of SOFCs.  相似文献   

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