Experimental verification for simulation study of Pt/CNT nanostructured cathode catalyst layer for PEM fuel cells

In this study, parametric study on the cathode catalyst layer in a Proton Exchange Membrane (PEM) fuel cell was conducted. Steady-state, two dimensional (2D) and nonisothermal conditions were proposed as critical hypotheses of work in essence. Multi-component mass diffusion along with convection mechanism in a single cell, conduction changes of proton and electron with experimental data and Knudsen diffusion which has a crucial impact on the simulation task in nanoscale, were considered in our study. Moreover, carbon nanotube (CNT), platinum (Pt) and Nafion loading effects as well as the porosity characteristics in a single-phase flow at different catalyst layer (CL) thicknesses were thoroughly investigated. The results presented herein, revealed that the amount of Pt and CNT has more profound effect than catalyst porosity. Based on the results derived, the model presented could be a promising mean to develop and construct a nanostructured catalyst layer. Meanwhile, our modified agglomerate model predicts the performance of fuel cell systems in different experimental conditions.     

Multichelate-functionalized carbon nanospheres used for immobilizing Pt catalysts for fuel cells

We have developed a covalent/coordinate strategy to immobilize Pt nanocrystals (average diameter 3.5 nm) on multichelate-functionalized carbon nanospheres (CNS). The method involves the covalent grafting of triethylenetetramine onto the CNS’ surface and the coordination of well-structured ethylenimine chains to Pt ions or atoms. The Pt-CNSs interface is probed with X-ray photoelectron spectroscopy to elucidate the nature of the chemical binding of ethylenimine to Pt. The Pt particle deposition can be easily controlled; to form separated and uniform Pt nanocrystals, or densely loaded Pt particles, depending on the molar ratio of Pt to amine groups. The Pt particle layer covered carbon exhibits significantly higher activity toward methanol oxidation (0.75 A mg⁻¹ cm⁻²) than commercial E-TEK 40% Pt loaded carbon with the corresponding data of 0.51 A mg⁻¹ cm⁻².     

Platinum/tin oxide/carbon cathode catalyst for high temperature PEM fuel cell

The performance of high temperature polymer electrolyte fuel cell (HT-PEMFC) using platinum supported over tin oxide and Vulcan carbon (Pt/SnOx/C) as cathode catalyst was evaluated at 160-200 °C and compared with Pt/C. This paper reports first time the Pt/SnOx/C preparation, fuel cell performance, and durability test up to 200 h. Pt/SnOx/C of varying SnO compositions were characterized using XRD, SEM, TEM, EDX and EIS. The face-centered cubic structure of nanosized Pt becomes evident from XRD data. TEM and EDX measurements established that the average size of the Pt nanoparticles were ∼6 nm. Low ionic resistances were derived from EIS, which ranged from 0.5 to 5 Ω-cm² for cathode and 0.05 to 0.1 Ω-cm² for phosphoric acid, doped PBI membrane. The addition of the SnOx to Pt/C significantly promoted the catalytic activity for the oxygen reduction reaction (ORR). The 7 wt.% SnO in Pt/SnO₂/C catalyst showed the highest electro-oxidation activity for ORR. High temperature PEMFC measurements performed at 180 °C under dry gases (H₂ and O₂) showed 0.58 V at a current density of 200 mA cm⁻², while only 0.40 V was obtained in the case of Pt/C catalyst. When the catalyst contained higher concentrations of tin oxide, the performance decreased as a result of mass transport limitations within the electrode. Durability tests showed that Pt/SnOx/C catalysts prepared in this work were stable under fuel cell working conditions, during 200 h at 180 °C demonstrate as potential cathode catalyst for HT-PEMFCs.     

Stability and durability of PtRu catalysts supported on carbon nanofibers for direct methanol fuel cells

The chemical stability and durability of PtRu catalysts supported on carbon nanofibers (CNFs) for the anode electrode of a direct methanol fuel cell (DMFC) are investigated by Pt and Ru dissolution tests in sulfuric acid and long-term performance tests of a single cell discharging at a constant current density of 150 mA cm⁻² for approximately 2000 h. A CNF with a herringbone-type structure, which is characterized by the alignment of graphene symmetrically angled to the fiber axis, was selected as the catalyst support because it has an edge-rich surface and a high surface area. In the metal dissolution test, the PtRu/CNF catalysts showed 1.5–2 times lower Ru leaching than a tested commercial catalyst (supported on activated carbon). The results of long-term performance tests also prove the higher durability of the anode catalyst compared with the commercial catalyst, when the anode polarization is compared before and after operation for 2000 h. Some analytical measurements, including X-ray diffraction, energy dispersive spectroscopy, and transmission electron microscopy were conducted to study the degradation of the catalyst activity.     

Electrocatalytic activity and durability study of carbon supported Pt nanodendrites in polymer electrolyte membrane fuel cells

In this paper, Pt nanodendrites are synthesized, and their use as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells is examined. When the Pt nanoparticles are shape-controlled in a dendritic form, the Pt nanoparticles exhibit a high mass activity that is nearly twice as high as the commercial Pt/C catalyst for the oxygen reduction reaction. This high activity is only achieved when the Pt nanodendrites are supported on carbon. The unsupported Pt nanodendrites exhibit very poor catalytic activity due to the limited accessibility of the active sites in the catalyst layer of the fuel cells. Based on the durability study of Pt nanodendrites, however, the dendritic structure is not stable during repeated potential cycling test and its structure collapse is the primary reason for the performance loss in the fuel cells.     

Improvement in the durability of carbon black-supported Pt cathode catalysts by silica-coating for use in PEFCs

Commercially available Pt metal catalysts supported on carbon black (Pt/CB) for polymer electrolyte fuel cell (PEFC) cathodes were covered with silica layers to improve their durability under the severe cathode operating conditions. The Pt metal particles in the Pt/CB catalyst grew in size during the accelerated durability tests (potential cycling between 0.6 and 1.0 V vs. RHE in an aqueous HClO₄ electrolyte). Thus, the Pt/CB catalyst was seriously deactivated for the oxygen reduction reaction over the course of the durability tests. In contrast, the silica layers, which wrapped around the Pt metal particles in the silica-coated Pt/CB catalyst, prevented the migration of the Pt metal particles on the carbon supports and the diffusion of Pt cations out of the silica layers. Thus, the silica-coated Pt/CB catalysts maintained a high activity for the oxygen reduction reaction over the course of the durability tests. In addition, the silica-coated Pt/CB prepared from methyltriethoxysilane showed a higher activity than that prepared from tetraethoxysilane. The porous structures and hydrophobicity of silica prepared from methyltriethoxysilane promoted the diffusion of oxygen and water molecules in the silica layers of the silica-coated Pt catalysts.     

Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell

The state-of-art understanding of durability issues (the degradation reasons and mechanisms, the influence of working conditions, etc.) of Pt-based catalysts for proton exchange membrane fuel cell (PEMFC) and the approaches for improving and studying catalyst durability are reviewed. Both carbon support and catalytic metals degrade under PEMFC conditions, respectively, through the oxidation of carbon and the agglomerate and the detachment from support materials of catalytic metals, especially under unnormal working conditions; furthermore, the degradation of carbon support and catalytic metals interact with and exacerbate one another. The working temperature, humidity, cell voltage (the electrode potential and the mode applied on the electrode), etc. can influence the catalyst durability. Carbons with high graphitization degree as support materials and alloying Pt with some other metals are proved to be effective ways to improve the catalyst durability. Time-effective and reliable methods for studying catalyst durability are indispensable for developing PEMFC catalysts.     

Modeling of PEM fuel cell Pt/C catalyst degradation

Pt/C catalyst degradation remains as one of the primary limitations for practical applications of proton exchange membrane (PEM) fuel cells. Pt catalyst degradation mechanisms with the typically observed Pt nanoparticle growth behaviors have not been completely understood and predicted. In this work, a physics-based Pt/C catalyst degradation model is proposed with a simplified bi-modal particle size distribution. The following catalyst degradation processes were considered: (1) dissolution of Pt and subsequent electrochemical deposition on Pt nanoparticles in cathode; (2) diffusion of Pt ions in the membrane electrode assembly (MEA); and (3) Pt ion chemical reduction in membrane by hydrogen permeating through the membrane from the negative electrode. Catalyst coarsening with Pt nanoparticle growth was clearly demonstrated by Pt mass exchange between small and large particles through Pt dissolution and Pt ion deposition. However, the model is not adequate to predict well the catalyst degradation rates including Pt nanoparticle growth, catalyst surface area loss and cathode Pt mass loss. Additional catalyst degradation processes such as new Pt cluster formation on carbon support and neighboring Pt clusters coarsening was proposed for further simulative investigation.     

Development of tellurium-modified carbon catalysts for oxygen reduction reaction in PEM fuel cells

Tellurium (Te)-modified carbon catalyst for oxygen reduction reaction was prepared through chemical reduction of telluric acid followed by the pyrolysis process at elevated temperatures. The catalyst was found to be active for oxygen reduction reaction. High-temperature pyrolysis plays a crucial role in the formation of the active sites of the catalysts. When the pyrolysis was conducted at 1000 °C, the catalyst exhibited the onset potential for oxygen reduction as high as 0.78 V vs. NHE and generated less than 1% H₂O₂ during oxygen reduction. The performance of the membrane–electrode assembly prepared with the Te-modified carbon catalyst was also evaluated.     

Investigation of the effect of graphitized carbon nanotube catalyst support for high temperature PEM fuel cells

In this study, it is aimed to investigate the graphitization effect on the performance of the multi walled carbon nanotube catalyst support for high temperature proton exchange membrane fuel cell (HT-PEMFC) application. Microwave synthesis method was selected to load Pt nanoparticles on both CNT materials. Prepared catalyst was analyzed thermal analysis (TGA), Transmission Electron Microscopy (TEM) and corrosion tests. TEM analysis proved that a distribution of Pt nanoparticles with a size range of 2.8–3.1 nm was loaded on the Pt/CNT and Pt/GCNT catalysts. Gas diffusion electrodes (GDE) were manufactured by an ultrasonic spray method with synthesized catalyst. Polybenzimidazole (PBI) membrane based Membrane Electrode Assembly (MEA) was prepared for observe the performance of the prepared catalysts. The synthesized catalysts were also tested in a HT-PEMFC environment with a 5 cm² active area at 160 °C without humidification. This study demonstrates the feasibility of using the microwave synthesis method as a fast and effective method for preparing high performance Pt/CNT and Pt/GCNT catalyst for HT-PEMFC. The HT-PEMFC performance evaluation shows current densities of 0.36 A/cm²0.30 A/cm² and 0.20 A/cm² for the MEAs prepared with Pt/GCNT, Pt/CNT and Pt/C catalysts @ 0.6 V operating voltage, respectively. AST (Accelerated Stress Test) analyzes of MEAs prepared with Pt/GCNT and Pt/CNT catalysts were also performed and compared with Pt/C catalyst. According to current density @ 0.6 V after 10,000 potential cycles, Pt/GCNT, Pt/CNT and Pt/C catalysts can retain 61%, 67% and 60% of their performance, respectively.     

Electrodeposition of PEM fuel cell catalysts by the use of a hydrogen depolarized anode

Up to 30% of the expensive catalyst metal in conventional fuel cell catalysts is not utilized in fuel cells caused by an absence of contact to either the ion conducting, electron conducting or educt phase. This contact can be improved by in situ electrodeposition with a precursor layer which is mostly done in a galvanostatic mode in the literature. In this paper electrochemical deposition with a hydrogen depolarized anode is described and so a potentiostatic electrodeposition under the control of the working-electrode potential and dry working-electrode conditions is enabled. This potentiostatic electrodeposition with a hydrogen depolarized anode significantly increases the performance of the fuel cell.     

Improved durability of SOEC stacks for high temperature electrolysis

An experimental study has been conducted at Idaho National Laboratory to demonstrate recent improvements in long-term durability of solid oxide electrolysis cells (SOEC) and stacks. Results of five stack tests are presented. Electrolyte-supported SOEC stacks were provided by Ceramatec Inc. and electrode-supported SOEC stacks were provided by Materials and Systems Research Inc. (MSRI), for these tests. Long-term durability tests were generally operated for durations of 1000 h or more. Stack tests based on technologies developed at Ceramatec and MSRI have shown significant improvement in durability in the electrolysis mode. Long-term degradation rates of 3.2%/khr and 4.6%/khr were observed for MSRI and Ceramatec stacks, respectively. One recent Ceramatec stack even showed negative degradation (performance improvement) over 1900 h of operation. Optimization of electrode and electrolyte materials, interconnect coatings, and electrolyte–electrode interface microstructures contribute to improve the durability of SOEC stacks.     

Effect of Pt loading on the hydrogen production of CNT/Pt composites functionalized with carboxylic groups

This work reports the morphological and photocatalytic hydrogen generation properties of CNT/Pt composites with and without functionalization by carboxylic/oxygen groups. The composites with and without functionalization were named f-CNT/Pt and CNT/Pt, respectively. Several f-CNT/Pt and CNT/Pt composites with different content of Pt NPs (from 0 to 30 wt%) were synthesized and analyzed by scanning electron microscopy (SEM). Those images revealed that the composites without functionalization presented higher agglomerations of Pt nanoparticles (NPs). Furthermore, the average sizes of the Pt NPs in the named f-CNT/Pt composites (2.3–2.9 nm) were lower than these in the CNT/Pt composites (2.5–3.1 nm). The hydrogen generation rates were also calculated from the decomposition of pure water under UV irradiation (365 nm) and found maximum values of 45.4 and 193.9 μmol·h⁻¹ g⁻¹ for the CNT/Pt and f-CNT/Pt composites (they contained 20 wt% of Pt NPs), respectively. Additional experiments for hydrogen generation were achieved using sodium sulfite as sacrificial agent; in this case, a maximum value of 13850 μmol·h⁻¹ g⁻¹ was obtained for the f-CNT/Pt composite. The f-CNT/Pt composites produced more hydrogen than the CNT/Pt composites because they presented higher content of defects; this was confirmed by the Raman spectra. We also showed that the Pt NPs acted as electron trap centers, which delayed the recombination of the photogenerated electrons and holes, this in turn, enhanced the hydrogen generation rates of the composites (the hydrogen generation was maximized by varying the content of Pt NPs deposited on the CNTs). The CNT/Pt composites presented here were simpler and easier to synthesize than the previous published ternary systems based on TiO₂, CNTs and Pt NPs.     

Efficient synthesis of Pt3Co/NC alloy catalysts with enhanced durability and activity for the oxygen reduction reaction

Lack of catalytic performance, short life, and high cost are three main problems related to JM-Pt/C catalysts for proton exchange membrane fuel cells. The introduction of cheap transition metals improves catalytic performance while significantly reducing the cost of the catalysts. Here, we report the synthesis of Pt₃Co/NC alloy catalysts via coating and pyrolysis treatment. The agglomeration of nanoparticles during the high-temperature alloying process is significantly inhibited by coating with PANI. Remarkably, the obtained Pt₃Co/NC alloy catalysts exhibit excellent ORR catalytic performance and structural stability in 0.1 mol/L HClO₄. After 30,000 potential cycles, the mass activity and area-specific activity of Pt₃Co/NC alloy catalysts are 1.949 and 3.936 times higher, respectively, than that of JM-Pt/C with negligible performance loss. The strong metal-support interaction between N and Pt and the Pt-rich surface restrict the dissolution of Pt and Co, resulting in excellent stability. This synthesis approach provides an effective way to develop active and stable Pt alloy catalysts.     

A review of the main parameters influencing long-term performance and durability of PEM fuel cells

This paper presents an overview of issues affecting the life and the long-term performance of proton exchange membrane fuel cells based on a survey of existing literature. We hope that this brief overview provides the engineers and researchers in the field with a perspective of the important issues that should be addressed to extend the life of next-generation fuel cells. Causes and fundamental mechanisms of cell degradation and their influence on long-term performance of fuel cells are discussed. Current research shows that main causes of short life and performance degradation are poor water management, fuel and oxidant starvation, corrosion and chemical reactions of cell components. Poor water management can cause dehydration or flooding, operation under dehydrated condition could damage the membrane whereas flooding facilitates corrosion of the electrodes, the catalyst layers, the gas diffusion media and the membrane. Corrosion products and impurities from outside can poison the cell. Thermal management is particularly important when the fuel cell is operated at sub-zero and elevated temperatures and is key at cold start-ups as well as when subjected to freezing conditions.     

A review of accelerated stress tests of MEA durability in PEM fuel cells

This paper is a review of recent work done on accelerated stress tests in the study of PEM fuel cell durability, with a primary focus on the main components of the membrane electrode assembly (MEA). The accelerated stressors for each component under different conditions are outlined, in an attempt to gain a detailed understanding of cell degradation with respect to microstructural change and performance attenuation in the perfluorosulfonic acid membrane, catalyst, and gas diffusion layers. Various techniques for evaluating the components' performance are presented, along with representative mitigation strategies. In addition, different degradation mechanisms proposed in recent publications are briefly reviewed.     

Carbon nanotube supported Pt-Ni catalysts for preferential oxidation of CO in hydrogen-rich gases

A series of carbon nano-tubes supported platinum-nickel catalysts were prepared and used for CO preferential oxidation in H₂-rich streams. The catalysts were characterized by using N₂-adsorption, XRD, HRTEM, H₂-TPD and H₂-TPR techniques. Effects of platinum and nickel loading amount, CO₂ and H₂O in the feed stream on the activity and selectivity over the catalysts were investigated. The results of catalytic performance tests show that the carbon nano-tubes supported Pt-Ni catalysts are very active and highly selective at low temperature for CO preferential oxidation in 1 vol. % CO, 1 vol. %O₂, 50 vol. % H₂ and N₂ gases. Adding 12.5 vol. % of CO₂ into the feed gases has slight negative influence on CO conversion. Adding 15 vol. % of H₂O leads to a little decrease of CO conversion at the temperature range of 100-120 °C, which is proposed to be caused by capillary wetting of water in the micro-pores of carbon nano-tubes. As the reaction temperature is higher, adding water can improve CO conversion. The characterization results indicate that platinum species are in nano-particles uniformly dispersed on the carbon nano-tubes surface. There are two kinds of nickel species, one is interacted with platinum and likely to form Pt-Ni alloy in reduction process, the other is much highly dispersed on carbon nano-tubes and strongly interacted with the supports. The high activity of the catalysts is attributed to the interaction between Pt and Ni with the formation of Pt-Ni alloy.     

Influence of the support in selective CO oxidation on Pt catalysts for fuel cell applications

One crucial requirement for the proton exchange membrane fuel cells (PEMFC) is to feed clean hydrogen to the anode, which is rapidly poisoned by traces of CO present from the upstream hydrocarbon reforming and water–gas shift processes. The removal of CO can be achieved by using catalysts able to selectively oxidize CO in the presence of excess hydrogen. Herein we report the effect of the support on Pt catalysts for total and selective oxidation (SELOX) of CO. The catalysts supported on ceria and zirconia presented higher activity than alumina and silica supported catalysts in SELOX reaction at low temperatures, but with lower CO conversions.     

Effect of N-doped carbon coatings on the durability of highly loaded platinum and alloy catalysts with different carbon supports for polymer electrolyte membrane fuel cells

An ideal oxygen reduction catalyst for use in fuel cells should exhibit both long-term durability and high activity. In this study, to increase the durability of highly loaded platinum- and platinum-nickel alloy catalysts possessing different types of carbon supports, a nitrogen-doped carbon shell was introduced on the catalyst surface through dopamine coating. As the catalyst surfaces were altered following shell formation, the ionomer contents of the catalyst inks were adjusted to optimise the three-phase boundary formation. Single cell tests were then conducted on these inks by applying them in a membrane electrolyte assembly. Furthermore, to confirm the durability of the catalysts under accelerated conditions, the operation was continued for 200 h at 70 °C and at a relative humidity of 100%. Transmission electron microscopy and electrochemical analysis were conducted before and after the durability tests, and the observed phenomena were discussed for catalysts bearing different types of carbon supports.