Jens Oluf Jensen

Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low-temperature fuel cells. A novel type of catalysts prepared by high-pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe3 C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide-based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts.

The CO Poisoning Effect in PEMFCs Operational at Temperatures up to 200°C

The CO poisoning effect on carbon-supported platinum catalysts (at a loading of 0.5 mg Pt/cm 2 per electrode) in polymer electrolyte membrane fuel cells (PEMFCs) has been investigated in a temperature range from 125 to 200°C with the phosphoric acid-doped polybenzimidazole membranes as electrolyte. The effect is very temperature-dependent and can be sufficiently suppressed at elevated temperature. By defining the CO tolerance as a voltage loss less than 10 mV, it is evaluated that 3% CO in hydrogen can be tolerated at current densities up to 0.8 A/cm 2 at 200°C, while at 125°C 0.1% CO in hydrogen can be tolerated at current densities lower than 0.3 A/cm 2 . For comparison, the tolerance is only 0.0025% CO (25 ppm) at 80°C at current densities up to 0.2 A/cm 2 . The relative anode activity for hydrogen oxidation was calculated as a function of the CO concentration and temperature. The effect of CO 2 in hydrogen was also studied. At 175°C, 25% CO 2 in the fuel stream showed only the dilution effect.

Fe3C-based oxygen reduction catalysts: synthesis, hollow spherical structures and applications in fuel cells

We present a detailed study of a novel Fe3C-based spherical catalyst with respect to synthetic parameters, nanostructure formation, ORR active sites and fuel cell demonstration. The catalyst is synthesized by high-temperature autoclave pyrolysis using decomposing precursors. Below 500 °C, melamine-rich microspheres are first developed with uniformly dispersed amorphous Fe species. During the following pyrolysis at temperatures from 600 to 660 °C, a small amount of Fe3C phase with possible Fe–Nx/C active sites are formed, however, with moderate catalytic activity, likely limited by the low conductivity of the catalyst. At high pyrolytic temperatures of 700–800 °C, simultaneous formation of Fe3C nanoparticles and encasing graphitic layers occur within the morphological confinement of the microspheres. With negligible surface nitrogen or iron functionality, the thus-obtained catalysts exhibit superior ORR activity and stability. A new ORR active phase of Fe3C nanoparticles encapsulated by thin graphitic layers is proposed. The activity and durability of the catalysts are demonstrated in both Nafion-based low temperature and acid doped polybenzimidazole-based high temperature proton exchange membrane fuel cells.

Synthesis and properties of poly(aryl sulfone benzimidazole) and its copolymers for high temperature membrane electrolytes for fuel cells

Poly(aryl sulfone benzimidazole) (SO2PBI) and its copolymers with poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole] (pPBI), termed as Co-SO2PBI, were synthesized with varied feeding ratios of 4,4′-sulfonyldibenzoic acid (SDBA) to terephthalic acid (TPA). Incorporation of the stiff para-phenylene and flexible aryl sulfone linkages in the macromolecular structures resulted in high molecular weight copolymers with good solubility. The chemical stability towards radical oxidation was improved for SO2PBI and its copolymer membranes due to the electron-withdrawing sulfone functional groups. Upon acid doping, the membrane swelling was reduced and the mechanical strength was improved, as compared with their meta structured analogues. At an acid doping level of 11 mol H3PO4 per average molar repeat unit, the Co-20%SO2PBI membrane exhibited a tensile strength of 16 MPa at room temperature and an H2-air fuel cell peak power density of 346 mW cm−2 at 180 °C at ambient pressure. Durability tests with the membrane under a constant current density of 300 mA cm−2 at 160 °C showed a degradation rate of 6.4 μV h−1 during a period of 2400 h, which was significantly lower than that for meta PBI membranes with a similar acid doping level.

Oxygen evolution catalysts on supports with a 3-D ordered array structure and intrinsic proton conductivity for proton exchange membrane steam electrolysis

Proton exchange membrane steam electrolyzers suffer from insufficient catalyst activity and durability due to the slow reaction kinetics for oxygen evolution reaction (OER) and poor durability under harsh operating environments. Aiming at enhancement of oxygen electrode kinetics and durability, composite support materials for iridium oxide are synthesized via in situ phosphorization reaction on tin doped indium oxide and possess functionalities of high electronic and intrinsic proton conductivity. At 130 °C under a water vapor atmosphere an overall conductivity of 0.72 S cm−1 is achieved with a contribution of around 10−2 S cm−1 proton conductivity. The support structure of three-dimensionally ordered hexagonal arrays displays a high specific surface area of 180 m2 g−1. Benefiting from the mixed conductivities and porous structure in the composite support materials, the supported IrO2 catalysts exhibit about five times enhancement of the OER activity in acidic electrolytes. The improved catalytic performance for the OER was further confirmed by PEM electrolyzer tests at 130 °C. A test of such a steam electrolyzer cell at 350 mA cm−2 shows good durability within a period of up to 1150 hours.

The electrochemical impedance of metal hydride electrodes

Abstract The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB 5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC equivalent circuits have been proposed in the literature. The experimental data, however, could not always be satisfactorily approximated. The approximation model presented here exhibits smooth fit to the experimental results for all frequencies in the whole range from 10 kHz to 0.1 mHz. Equivalent circuits, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were observed. The impedance analysis was found to be an efficient method for characterizing metal hydride electrodes in situ.

High temperature polymer electrolyte membrane fuel cells: Approaches, status, and perspectives

perspectives DTU Orbit (08/11/2019) High temperature polymer electrolyte membrane fuel cells: Approaches, status, and perspectives This book is a comprehensive review of high-temperature polymer electrolyte membrane fuel cells (PEMFCs). PEMFCs are the preferred fuel cells for a variety of applications such as automobiles, cogeneration of heat and power units, emergency power and portable electronics. The first 5 chapters of the book describe rationalization and illustration of approaches to high temperature PEM systems. Chapters 6 13 are devoted to fabrication, optimization and characterization of phosphoric acid-doped polybenzimidazole membranes, the very first electrolyte system that has demonstrated the concept of and motivated extensive research activity in the field. The last 11 chapters summarize the state-of-the-art of technological development of high temperature-PEMFCs based on acid doped PBI membranes including catalysts, electrodes, MEAs, bipolar plates, modelling, stacking, diagnostics and applications.

Niobium phosphates as an intermediate temperature proton conducting electrolyte for fuel cells

A new proton conductor based on niobium phosphates was synthesized using niobium pentoxide and phosphoric acid as precursors. The existence of hydroxyl groups in the phosphates was confirmed and found to be preserved after heat treatment at 500 °C or higher, contributing to an anhydrous proton conductivity of 1.6 × 10−2 S cm−1 at 250 °C. The conductivity increased with water content in the atmosphere and reached 5.8 × 10−2 S cm−1 under pure water vapour at the same temperature. The conductivity showed good stability in the low water partial pressure range of up to 0.05 atm. The metal phosphates are of high interest as potential proton conducting electrolytes for fuel cells operational in an intermediate temperature range.

Direct Synthesis of Fe3C‐Functionalized Graphene by High Temperature Autoclave Pyrolysis for Oxygen Reduction

We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3 C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested as an electrocatalyst, the graphene-based composite exhibited excellent catalytic activity towards the oxygen reduction reaction in alkaline solution with an onset potential of ca. 1.05 V (vs. the reversible hydrogen electrode) and a half-wave potential of 0.83 V, which is comparable to the commercial Pt/C catalyst.

Structural studies of disordered Mg2NiH4 formed by mechanical grinding

The low temperature phase of Mg2NiH4 was mechanically ground in argon atmosphere. The ordered monoclinic structure was destroyed to form the disordered cubic structure, previously only found above 510 K. With a Guinier-Hagg X-ray camera the cell parameter was determined to be a=6.492(3) A. By performing a Rietveld refinement on neutron diffraction data it was confirmed that the disordered structure is similar to the high temperature form of Mg2NiH4 (space group Fm3m).