| 1. |
- Gode, Peter, et al.
(författare)
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In-situ measurements of gas permeability in fuel cell membranes using a cylindrical microelectrode
- 2002
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Ingår i: Journal of Electroanalytical Chemistry. - 0022-0728 .- 1873-2569. ; 518:2, s. 115-122
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Tidskriftsartikel (refereegranskat)abstract
- A new method to study permeation of gases in proton conducting membranes using a cylindrical microelectrode is presented. The focus of this work was to develop an in-situ method to study transport properties of hydrogen and oxygen close to real fuel cell operating conditions. The gas permeability is strongly affected by the change of water content in the membrane and it is therefore of advantage that, by using this method, measurements can be carried out over a wide range of relative humidities. The numerical method makes it possible to separate the diffusion coefficient and the concentration of dissolved gas in the membrane and also allows kinetic limitations to be taken into account. Chronoamperometric measurements on Nafion(R) 117 were successfully evaluated numerically. Experiments at temperatures of 25 and 60 degreesC with respect to oxygen permeation and at 60 degreesC for hydrogen permeation at relative humidities in the range 30-94% are presented. The reproducibility of data was excellent when measuring with different microelectrodes, on the same membrane sample, but differed when measuring on different samples. In general, the permeability increases with increasing temperature and relative humidity.
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| 2. |
- Gode, Peter, et al.
(författare)
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Influence of the composition on the structure and electrochemical characteristics of the PEFC cathode
- 2003
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 48:28, s. 4175-4187
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Tidskriftsartikel (refereegranskat)abstract
- The influence the composition of the cathode has on its structure and electrochemical performance was investigated for a Nafion content spanning from 10 to 70 wt.%. The cathodes were formed on a Nafion membrane by the spray method and using 20 wt.% Pt on Vulcan (E-TEK). Materials characterisation (SEM, STEM, gas and mercury porosimetry, electron conductivity) and electrochemical characterisation (steady-state polarisation curve, impedance spectroscopy in O-2 and current-pulse measurements in N-2) were performed. The impedance spectra were analysed using our dynamic agglomerate model. The results indicate that the agglomerate model is valid until a Nafion content of about 45 wt.%. Pt/C and Nation are homogeneously mixed for any composition and no Nafion film was observed. The cathodes containing 36-43 wt.% Nation display a single or double Tafel slope behaviour ascribed to diffusion limitations in the agglomerates. At larger Nation content, the agglomerate model can describe the curves only by assuming a diffusion coefficient 3-4 decades smaller than that of gases. At such compositions, the porosity was only 10%. These results were interpreted as a blocking of the pores and a non-percolating pore system for too large Nafion contents.
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| 3. |
- Gode, Peter, et al.
(författare)
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Membrane Durability in a PEM Fuel Cell Studied Using PVDF Based Radiation Grafted Membranes
- 2003
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Ingår i: Fuel Cells. - : Wiley. - 1615-6846 .- 1615-6854. ; 3:1-2, s. 21-27
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Tidskriftsartikel (refereegranskat)abstract
- The durability testing of membranes for use in a polymer electrolyte fuel cell (PEFC) has been studied in situ by a combination of galvanostatic steady-state and impedance measurements. The PEFC measurements, which are time consuming, have been compared to fast ex situ testing in 3% H2O 2 solution. For the direct assessment of membrane degradation micro-Raman spectroscopy and determination of ion exchange capacity (IEC) have been used. PVDF based membranes, radiation grafted with styrene and sulfonated, were used as model membranes. By using low degrees of grafting, below about 35%, the durability of this type of membrane can be increased. Degradation in the fuel cell was found to be highly localised. It was found that in situ measurements in the PEFC alone are not sufficient. Measurement of the cell resistance via impedance is not always a reliable indicator of changes in membrane resistance because other resistance changes in the cell can easily interfere and cannot be separated from those caused by the membrane. Micro-Raman is an ideal complementary method to in situ testing, but it is time consuming. For fast pre-screening of membrane durability mass loss measurements during exposure to 3% H2O2 solution combined with the determination of changes in the IEC can be performed.
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| 4. |
- Bergman, B., et al.
(författare)
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Contact corrosion resistance between the cathode and current collector plate in the molten carbonate fuel cell
- 2001
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 148:1, s. A38-A43
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Tidskriftsartikel (refereegranskat)abstract
- The corrosion layer Formed in the contact between the cathode and the current collector is one factor limiting the cathode performance in molten carbonate fuel cells (MCFC). In order to investigate the contribution to the total polarization of the contact resistance, electrochemical experiments were performed in a laboratory-scale fuel cell unit with a specially designed current collector. Two cathode materials, NiO and LiCoO2, were investigated to elucidate the impact of the cathode material on the formed corrosion layer. Polarization measurements as well as electrochemical impedance spectroscopy were used. The method works well for NiO electrodes. However, due to the poor electronic conductivity in the LiCoO2 electrode, the experimental results become difficult to evaluate due to a nonuniform potential distribution. The contact resistance between the cathode and the current collector contributes with a large value to the total cathode polarization. The corrosion layer in case of the LiCoO2 cathode was iron-rich and has a thickness of about 20 mum after 8 weeks operation of the fuel cell. Ln the case of the NiO cathode, a nickel-rich corrosion layer of about 15 mum was formed after 5 weeks operation of the fuel cell.
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| 5. |
- Birgersson, E., et al.
(författare)
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Reduced two-dimensional one-phase model for analysis of the anode of a DMFC
- 2003
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 150:10, s. A1368-A1376
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Tidskriftsartikel (refereegranskat)abstract
- An isothermal two-dimensional liquid phase model for the conservation of mass, momentum, and species in the anode of a direct methanol fuel cell (DMFC) is presented and analyzed. The inherent electrochemistry in the DMFC anode active layer is reduced to boundary conditions via parameter adaption. The model is developed for the case when the geometry aspect ratio is small, and it is shown that, under realistic operating conditions, a reduced model, which nonetheless describes all the essential physics of the full model, can be derived. The significant benefits of this approach are that physical trends become much more apparent than in the full model and that there is considerable reduction in the time required to compute numerical solutions, a fact especially useful for wide-ranging parameter studies. Such a study is then performed in terms of the three nondimensional parameters that emerge from the analysis, and we subsequently interpret our results in terms of the dimensional design and operating parameters. In particular, we highlight their effect on methanol mass transfer in the flow channel and on the current density. The results indicate the relative importance of mass-transfer resistance in both the flow channel and the adjacent porous backing.
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| 6. |
- Birgersson, Erik, et al.
(författare)
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Reduced two-phase model for analysis of the anode of a DMFC
- 2004
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 151:12, s. A2157-A2172
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Tidskriftsartikel (refereegranskat)abstract
- An isothermal two-phase ternary mixture model that takes into account conservation of momentum, mass, and species in the anode of a direct methanol fuel cell (DMFC) is presented and analyzed. The slenderness of the anode allows a considerable reduction of the mathematical formulation, without sacrificing the essential physics. The reduced model is then verified and validated against data obtained from an experimental DMFC outfitted with a transparent end plate. Good agreement is achieved. The effect of mass-transfer resistances in the flow field and porous backing are highlighted. The presence of a gas phase is shown to improve the mass transfer of methanol at higher temperatures (>30 degreesC). It is also found that at a temperature of around 30 degreesC, a one-phase model predicts the same current density distribution as a more sophisticated two-phase model. Analysis of the results from the two-phase model, in combination with the experiments, results in a suggestion for an optimal flow field for the liquid-fed DMFC.
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| 7. |
- Brown, Shelley, et al.
(författare)
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Characterisation and modelling of a high-power density lithium-ion positive electrode for HEV application
- 2004
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Konferensbidrag (refereegranskat)abstract
- In this study, the impedance response of a porous electrode based on LiNi0.8Co0.15Al0.05O2 was investigated using an impedance model including the following features: Butler-Volmer kinetics; double layer capacitance; solid phase concentration and potential gradients; electrolyte phase concentration and potential according to the concentrated electrolyte theory; particle size distribution; and an empirical relation between equilibrium potential and state of charge. The model was evaluated by fitting it to experimental results using different electrolytes and states of charge. In addition, the characteristic parameters for the electrode were obtained from the fitting results.
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| 8. |
- Byrne, P., et al.
(författare)
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A simulation of the tertiary current density distribution from a chlorate cell - I. Mathematical model
- 2001
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 148:10, s. D125-D132
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Tidskriftsartikel (refereegranskat)abstract
- Numerical modeling is becoming an integral part of all research and development within the field of electrolytic systems. A numerical model that calculates the current density distribution and concentration profiles of a chlorate cell is presented here, The results are shown as functions of electrolyte velocity and exchange current density. The model takes into account the three transport mechanisms; diffusion, migration, and convection by considering the development of the flow velocity vector through the channel. It was seen that the developing velocity profile influences the concentration overpotentials, which in turn influences current density distributions. Results from the model show that the total current density decreased along the length of the anode, and that this distribution varied more at lower velocities. In addition, it was seen that migration contributes significantly to species transport, even within the diffusion layer. Finally, the model indicates that the hypochlorite ion is the main participant in the principal side reaction producing oxygen, and not the hypochlorous acid molecule. The results are useful as they increase knowledge of the chlorate process, and can be used to simulate future systems with a wide range of varying parameters such as cell geometry, flow, electrolyte composition, and electrode materials. The aim of the model is to use it as a tool for identifying the sources that contribute to the overpotential in the cell. This article concentrates on the concentration overpotential, which is one of the phenomena that can actually be influenced,
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| 9. |
- Cornell, Ann, et al.
(författare)
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Ruthenium-based dimensionally stable anode in chlorate electrolysis - Effects of electrolyte composition on the anode potential
- 2003
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 150:1, s. D6-D12
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Tidskriftsartikel (refereegranskat)abstract
- In this work the anodic reactions taking place on a dimensionally stable anode (DSA) in chlorate electrolyte have been investigated. Rotating disk electrodes were made from commercial RuO2-catalyzed DSAs and studied in steady-state polarization measurements, mainly IR-corrected polarization curves. Effects of varying pH and electrolyte concentrations of chloride, chlorate, chromium(VI), hypochlorite (ClO- + ClOH) as well as mass transport were studied. The kinetics for the chlorine evolution reaction, with a Tafel slope of 40 mV/decade of current, was not dependent on pH in the region 2-8, at potentials lower than 1.2 V vs. Ag/AgCl. The slope of the polarization curves increased at about 1.2 V vs. Ag/AgCl, a pH-dependent bend not due to mass-transport limitations in the electrolyte. At a pH of 6.5, typical for the chlorate process, oxygen evolution is an important side reaction favored by the dichromate buffer and by increased mass transport, both keeping down the pH at the anode. In the chlorine evolution region the potentials increased when adding Cr(VI) to the electrolyte, whereas no major effect was seen from additions of NaClO. (C) 2002 The Electrochemical Society.
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| 10. |
- Cornell, Ann, et al.
(författare)
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Ruthenium based DSA in chlorate electrolysis–critical anode potential and reaction kinetics
- 2003
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Ingår i: Electrochimica Acta. - 0013-4686 .- 1873-3859. ; 48:5, s. 473-481
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Tidskriftsartikel (refereegranskat)abstract
- Ruthenium based DSA®s have been investigated in chlorate electrolyte using rotating discs made from commercial electrodes. Measurements of the voltammetric charge, q*, and of iR-corrected polarisation curves up to current densities of 40 kA/m2 were recorded on new anodes and on aged anodes from 3 years of production in a chlorate plant. Anodic polarisation curves in chloride containing electrolytes bend towards a higher slope at approximately 1.2 V versus Ag/AgCl, likely due to oxidation of ruthenium. The potential and current density at which the curves bend have been defined as the critical potential, Ecr, and the critical current density, icr. New anodes that operate at a relatively high potential, >Ecr, obtain an increase in real surface area and thereby a decrease in anode potential and in the selectivity for oxygen formation during the first months of operation. Experiments at constant ionic strength under chlorate process conditions showed that Ecr decreased with increasing chloride concentration with a factor of −0.09 V/log Cl−, whereas icr increased with increasing chloride concentration. The chlorine evolution reaction was of the first order with respect to chloride concentration. A possible reaction mechanism for chlorine formation is suggested.
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