Browsing by Author "Hashimoto, T."
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- Characterization of MEA degradation for an open air cathode PEM fuel cellPublication . Silva, R. A.; Hashimoto, T.; Thompson, G. E.; Rangel, C. M.As fuel cell technology matures and time scale to commercialization decreases, the need for a more comprehensive knowledge of materials’ aging mechanisms is essential to attain specified lifetime requirements for applications. In this work, the membrane electrode assembly (MEA) degradation of an eight-cell PEM low power stack was evaluated, during and after fuel cell aging in specified testing conditions of load-cycling that may compromise the durability of the catalyst. The stack degradation analysis comprised observation of catalytic layers, morphology and composition. Examination of the MEAs cross sections, in a joint SEM and TEM study, revealed thickness variation of catalytic layer (up to 47% for the cathode layers), and cracking, delamination, and catalyst migration were observed even though catalyst sintering and consequent loss of electrochemical active area seem to be predominant together with F loss from the ionomer used as binder in the catalytic layers.
- Hydrogen production from sodium borohydride on a Ni-Ru catalyst : an electrochemical studyPublication . Rangel, C. M.; Fernandes, Vitor; Ferreira, M. J. F.; Pinto, A. M. F. R.; Hashimoto, T.; Thompson, G. E.Previous work by the authors has demonstrated a high rate and high yield hydrolysis of sodium borohydride, in the presence of a Ni-Ru catalyst synthesized by wet chemistry. The catalyst has been fully characterized and utilized more than 300 times exhibiting high stability and durability. In this work, results of an electrochemical study are reported using the powder catalyst supported on a Ni foam in order to measure the open circuit potential during hydrogen production and to study the reaction using voltammetry and ac impedance. Production rates were as high as 10 Lmin-1gcat -1 at 65ºC. Electrochemical studies indicated that the hydrogen evolution mechanism corresponds to a Volmer- Heyrovsky type, suggested by a Tafel slope of 117 mVdec-1. Tafel region potentials are in agreement with values found for hydrolysis at the open circuit. The Langmuir-Hinshelwood mechanism explains the hydrolysis of sodium borohydride using a Ni-Ru catalyst. The role of Ni and Ru is briefly discussed.
- Materials degradation mechanisms in an open cathode low power PEM Fuel CellPublication . Rangel, C. M.; Paiva Luís, Teresa; Hashimoto, T.; Thompson, G. E.In this work, a low power PEM fuel cell intended for passive management of water was operated integrating a range of relative humidity (RH) from 30 to 80% and temperatures from 5 to 55ºC. An open air cathode, provided with an excess air stoichiometry condition, was designed for easy water removal and stack cooling. The 4 cell stack was fed with pure hydrogen and uses own design flow field drawn on graphite plates from Schunk and a commercial MEA with carbon supported catalyst containing 0.3 mgcm-2 Pt. Full stack characterization was made using a purpose-built test station and a climatic chamber with temperature and RH control. Results indicated that 60% RH is associated to maximum performance on the fuel cell under study over the studied temperature range. While water management is done in a passive fashion, heat management is accomplished on the basis of the injection of air at the cathode with the fuel cell showing good performances at relatively low currents where back diffusion towards the anode is favored.
- MEA degradation in PEM Fuel Cell : a joint SEM and TEM studyPublication . Silva, R. A.; Hashimoto, T.; Thompson, G. E.; Rangel, C. M.One of the important factors determining the lifetime of polymer electrolyte membrane fuel cells (PEMFCs) is membrane electrode assembly (MEA) degradation and failure. The lack of effective mitigation methods is largely due to the currently very limited understanding of the underlying mechanisms for mechanical and chemical degradations of fuel cell MEAs. This work reports on the effect of 1500 h operation of an eight-cell stack Portuguese prototype low power fuel cell. A performance decrease of 34%, in terms of maximum power, was found at the end of testing period. A post-mortem analysis by SEM and TEM was done for most cells of the fuel cell. Loss of the PTFE ionomer in the anode and cathode catalytic layers; morphological changes in the catalyst surfaces such as loss of porosity and platinum aggregation, deformation on the MEA components (anode, cathode and membrane) were identified. Others, like delamination and cracking were also detected. Catalyst migration and agglomeration on the interface of the electrodes was observed at cells 2, 4, 6 and 7. A platinum band was also detected on the membrane at 2 μm apart from the anode of cell 4. In some cases, dissolution occurred with re-deposition of the platinum particles with facet
- Platinum instability in PEM fuel cells MEA’s subjected to chloride contaminationPublication . Rangel, C. M.; Paiva Luís, Teresa; Hashimoto, T.; Thompson, G. E.In this work a low power fuel cell, intended for passive management of water, was operated integrating a range of relative humidity (RH) from ~30 to 80% and temperatures from 5 to 55 ºC. The stack was fed with pure hydrogen. An open air cathode was designed for easy water removal and stack cooling. The stack uses own design flow field drawn on graphite plates from Schunk and a commercial MEA with carbon supported catalyst containing 0.3 mgcm-2 Pt. Polarization curves were registered for a full stack characterization using a purpose-built test station and a climatic chamber with temperature and RH control. Results indicated that 60% RH is associated to maximum fuel cell performance over the studied temperature range. While water management is done in a passive fashion, heat management is done on the basis of the injection of air at the cathode with the fuel cell showing good performances at relatively low currents where back diffusion towards the anode is favored. The loss of performance with temperature increase was related to an increase in the membrane resistance which may correspond to loss of water on the anode side. Performances at temperatures lower that room temperature showed only slight decrease in power. An examination of the fuel cell components after 100 h of operation revealed that chloride contamination has produced cathode failure associated to catalyst migration anomalies favored by operation conditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte. Migration resulted in precipitation with larger mean particle size distribution within the solid electrolyte when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material. Coarsening of platinum particles occurs at nano and micro-scale. The mechanism for the lost of catalyst by dissolution and growth is discussed on the basis of a joint electrochemical and SEM/TEM study.
- The effect of chloride as catalyst layer contaminant on the degradation of PEMFCsPublication . Paiva Luís, Teresa; Hashimoto, T.; Plancha, Maria João; Thompson, G. E.; Rangel, C. M.In this work, the effect of chloride as a catalyst contaminant was studied on the performance and durability of a low power open-cathode fuel cell, intended for passive management of water. In an ex-situ study, cyclic voltammetry was used to assess the redox behaviour of platinum in chloride contaminated solutions at room temperature.The cell was operated integrating a range of relative humidity (RH) from ~30 to 80% and temperatures from 5 to 55 ºC. Results indicated that 60% RH is associated to maximum fuel cell performance over the studied temperature range. An examination of the fuel cell components after 100 h of operation revealed that chloride contamination has produced cathode failure associated to catalyst migration favored by operation conditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte. Migration resulted in precipitation with larger mean particle size distribution within the solid electrolyte when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material.