Tese de doutoramento. Engenharia Química e Biológica. Universidade do Porto. Faculdade de Engenharia. 2011

Tese de doutoramento. Engenharia Química e Biológica. Faculdade de Engenharia. Universidade do Porto. 2009

The anisotropic mass transport issues inside a fuel cell membrane have been studied in this thesis using computer modelling. The polymer electrolyte membrane (PEM) conductivity of a PEM fuel cell (PEMFC) depends on the hydration state of the hydrophilic charged sites distributed in the pores of the membrane. Water humidification of these charged sites is crucial for sustaining the membrane conductivity and reducing concerning voltage losses of the cell. During the operation of a PEMFC, the transport of humidified inlet gases (fuel/oxidant) is influenced by external design factors such as flow field plate geometry of the gas circulating channels. As a result, there arises a distribution in the mass transport of water inside the membrane electrode assembly. A two-dimensional, cross-the-channel, fuel cell membrane layer mass transport model, developed in this work, helps the study of the impact of factors causing the distribution in the membrane ionic conductivity on ohmic losses.<p>The governing equations of the membrane mathematical model stem from the multicomponent framework of concentrated solution theory. All mass transport driving forces within the vapour and/or liquid equilibrated phases have been accounted in this research. A computational model, based on the finite control volume method, has been implemented using a line-by-line approach for solving the dependent variables of the mass transport equations in the two-dimensional membrane domain. The required boundary conditions for performing the anisotropic mass transport analysis have been obtained from a detailed agglomerate model of the cathode catalyst layer available in the literature.<p>The results obtained using boundary conditions with various flow field plate channel-land configurations revealed that the anisotropic water transport in the cathode half-cell severely affects the ohmic losses within the membrane. A partially humidified vapour equilibrated membrane simulation results show that a smaller channel-land ratio (1:1) sustains a better membrane performance compared to that with a larger one (2:1 or 4:1). Resistance calculations using the computer model revealed that ohmic losses across the membrane also depend on its physical parameters such as thickness. It was observed that the resistance offered by a thinner membrane towards vapour phase mass transport is comparatively lower than that offered by a thicker membrane. A further analysis accounting the practical aspects such as membrane swelling constraints, imposed by design limitations of a fuel cell, revealed that the membrane water content and ionic conductivity are altered with an increase in the compression constraint effects acting upon a free swelling membrane.

The anisotropic mass transport issues inside a fuel cell membrane have been studied in this thesis using computer modelling. The polymer electrolyte membrane (PEM) conductivity of a PEM fuel cell (PEMFC) depends on the hydration state of the hydrophilic charged sites distributed in the pores of the membrane. Water humidification of these charged sites is crucial for sustaining the membrane conductivity and reducing concerning voltage losses of the cell. During the operation of a PEMFC, the transport of humidified inlet gases (fuel/oxidant) is influenced by external design factors such as flow field plate geometry of the gas circulating channels. As a result, there arises a distribution in the mass transport of water inside the membrane electrode assembly. A two-dimensional, cross-the-channel, fuel cell membrane layer mass transport model, developed in this work, helps the study of the impact of factors causing the distribution in the membrane ionic conductivity on ohmic losses.<p>The governing equations of the membrane mathematical model stem from the multicomponent framework of concentrated solution theory. All mass transport driving forces within the vapour and/or liquid equilibrated phases have been accounted in this research. A computational model, based on the finite control volume method, has been implemented using a line-by-line approach for solving the dependent variables of the mass transport equations in the two-dimensional membrane domain. The required boundary conditions for performing the anisotropic mass transport analysis have been obtained from a detailed agglomerate model of the cathode catalyst layer available in the literature.<p>The results obtained using boundary conditions with various flow field plate channel-land configurations revealed that the anisotropic water transport in the cathode half-cell severely affects the ohmic losses within the membrane. A partially humidified vapour equilibrated membrane simulation results show that a smaller channel-land ratio (1:1) sustains a better membrane performance compared to that with a larger one (2:1 or 4:1). Resistance calculations using the computer model revealed that ohmic losses across the membrane also depend on its physical parameters such as thickness. It was observed that the resistance offered by a thinner membrane towards vapour phase mass transport is comparatively lower than that offered by a thicker membrane. A further analysis accounting the practical aspects such as membrane swelling constraints, imposed by design limitations of a fuel cell, revealed that the membrane water content and ionic conductivity are altered with an increase in the compression constraint effects acting upon a free swelling membrane.

In this work characterisation methods and fuel cell hardwarewere developed for studying the components of the polymerelectrolyte fuel cell (PEFC). Humidifiers and other componentswere tested in order to develop reproducible and reliableexperimental techniques. A set-up for testing larger cells andstacks was developed. A new type of polymer electrolyte membrane fuel cell wasdeveloped for laboratory investigations. Current collectormaterial and gas flow channels can easily be modified in thisconstruction. The electrode potentials can be measured at thegas backing layers, thereby allowing measurement of contactresistances. The use of a reference electrode is alsopossible. Contact resistances were studied in situ as a function oftime, clamping pressure, gas pressure and current density.Ex-situ measurements were used to validate the in-situ contactresistance measurements. The validity and error sources of theapplied in-situ measurement methods with reference electrodesand potential probes were studied using both computersimulations and experiments. An in-house membrane electrode assembly (MEA) productionline was developed. In-house produced MEAs were utilised inboth membrane degradation and mass transport studies. The durability testing of PVDF based membranes membranes wasstudied both by fuel cell experiments and ex-situ testing.Raman spectra were measured for used membranes. A current distribution measurement method was developed. Theeffect of inlet humidification and gas composition at thecathode side was studied. In addition, two different flow fieldgeometries were studied. The results of current distributionmeasurements were used to validate a PEFC model. Methods for characterising gas diffusion layer (GDL)performance by fuel cell testing and ex-situ measurements weredeveloped. The performance of GDL materials was tested withvarying cell compression and cathode humidity. Porosity, poresize distribution and contact angle were determined. Electricalcontact resistance, thermal impedance and gas permeabilitieswere measured at different compression levels. Development work on a stack with stainless steel net wascarried out as well as characterisation studies of differentstack components. Thermal impedances and flow fieldpermeability were measured. Mass transport limitations in the cathodes were studied byvarying the electrode thickness, partial pressure and humidityof oxygen. <b>Keywords:</b>polymer electrolyte membrane fuel cell (PEFC),contact resistance, clamping pressure, stainless steel,membrane degradation, current distribution, gas diffusionlayer, stack, thermal impedance, permeability.

This project is aimed at developing and demonstrating highly conductive, lightweight, and low-cost thermoplastic blends to be used as flow field bipolar plates for polymer electrolyte membrane (PEM) fuel cells. <br><br> The research is focused on designing, prototyping, and testing carbon-filled thermoplastic composites with high electrical conductivity, as well as suitable mechanical and process properties. <br><br> The impact of different types of fillers on the composite blend properties was evaluated, as well as the synergetic effect of mixtures of fill types within a thermoplastic polymer matrix. A number of blends were produced by varying the filler percentages. Composites with loadings up to 65% by weight of graphite, conductive carbon black, and carbon fibers were investigated. Research results show that three-filler composites exhibit better performance than single or two-filler composites. <br><br> Injection and compression molding of the conductive carbon filled polypropylene blend was used to fabricate the bipolar plates. A Thermal Gravimetric Analysis (TGA) was used to determine the actual filler loading of composites. A Scanning Electron Microscope (SEM) technique was use as an effective way to view the microstructure of composite for properties such as edge effects, porosity, and fiber alignment. Density and mechanical properties of conductive thermoplastic composites were also investigated. During this study, it was found that 1:1:1 SG-4012/VCB/CF composites showed better performance than other blends. The highest conductivity, 1900 S/m in in-plane and 156 S/m in through plane conductivity, is obtained with the 65% composite. Mechanical properties such as tensile modulus, tensile strength, flexural modulus and flexural strength for 65% 1:1:1 SG-4012/VCB/CF composite were found to be 584. 3 MPa, 9. 50 MPa, 6. 82 GPa and 47. 7 MPa, respectively, and these mechanical properties were found to meet minimum mechanical property requirements for bipolar plates. The highest density for bipolar plate developed in this project is 1. 33 g/cm³ and is far less than that of graphite bipolar plate. <br><br> A novel technique for metal insert bipolar plate construction was also developed for this project. With a copper sheet insert, the in-plane conductivity of bipolar plate was found to be significantly improved. The performance of composite and copper sheet insert bipolar plates was investigated in a single cell fuel cell. All the composites bipolar plates showed lower performance than the graphite bipolar plate on current-voltage (I-V) polarization curve testing. Although the copper sheet insert bipolar plates were very conductive in in-plane conductivity, there was little improvement in single cell performance compared with the composite bipolar plates. <br><br> This work also investigated the factors affecting bipolar plate resistance measurement, which is important for fuel cell bipolar plate design and material selection. Bipolar plate surface area (S) and surface area over thickness (S/T) ratio was showed to have significant effects on the significance of interfacial contact resistances. At high S/T ratio, the contact resistance was found to be most significant for thermoplastic blends. Other factors such as thickness, material properties, surface geometry and clamping pressure were also found to affect the bipolar plate resistance measurements significantly.

This project is aimed at developing and demonstrating highly conductive, lightweight, and low-cost thermoplastic blends to be used as flow field bipolar plates for polymer electrolyte membrane (PEM) fuel cells. <br><br> The research is focused on designing, prototyping, and testing carbon-filled thermoplastic composites with high electrical conductivity, as well as suitable mechanical and process properties. <br><br> The impact of different types of fillers on the composite blend properties was evaluated, as well as the synergetic effect of mixtures of fill types within a thermoplastic polymer matrix. A number of blends were produced by varying the filler percentages. Composites with loadings up to 65% by weight of graphite, conductive carbon black, and carbon fibers were investigated. Research results show that three-filler composites exhibit better performance than single or two-filler composites. <br><br> Injection and compression molding of the conductive carbon filled polypropylene blend was used to fabricate the bipolar plates. A Thermal Gravimetric Analysis (TGA) was used to determine the actual filler loading of composites. A Scanning Electron Microscope (SEM) technique was use as an effective way to view the microstructure of composite for properties such as edge effects, porosity, and fiber alignment. Density and mechanical properties of conductive thermoplastic composites were also investigated. During this study, it was found that 1:1:1 SG-4012/VCB/CF composites showed better performance than other blends. The highest conductivity, 1900 S/m in in-plane and 156 S/m in through plane conductivity, is obtained with the 65% composite. Mechanical properties such as tensile modulus, tensile strength, flexural modulus and flexural strength for 65% 1:1:1 SG-4012/VCB/CF composite were found to be 584. 3 MPa, 9. 50 MPa, 6. 82 GPa and 47. 7 MPa, respectively, and these mechanical properties were found to meet minimum mechanical property requirements for bipolar plates. The highest density for bipolar plate developed in this project is 1. 33 g/cm³ and is far less than that of graphite bipolar plate. <br><br> A novel technique for metal insert bipolar plate construction was also developed for this project. With a copper sheet insert, the in-plane conductivity of bipolar plate was found to be significantly improved. The performance of composite and copper sheet insert bipolar plates was investigated in a single cell fuel cell. All the composites bipolar plates showed lower performance than the graphite bipolar plate on current-voltage (I-V) polarization curve testing. Although the copper sheet insert bipolar plates were very conductive in in-plane conductivity, there was little improvement in single cell performance compared with the composite bipolar plates. <br><br> This work also investigated the factors affecting bipolar plate resistance measurement, which is important for fuel cell bipolar plate design and material selection. Bipolar plate surface area (S) and surface area over thickness (S/T) ratio was showed to have significant effects on the significance of interfacial contact resistances. At high S/T ratio, the contact resistance was found to be most significant for thermoplastic blends. Other factors such as thickness, material properties, surface geometry and clamping pressure were also found to affect the bipolar plate resistance measurements significantly.

Polymer electrolyte membrane fuel cells (PEMFCs) have the potential to play a major role as energy generators for transportation and portable applications. One of the current barriers to their commercialization is the cost of the components and manufacturing, specifically the bipolar plates. One approach to preparing PEMFCs for commercialization is to develop new bipolar plate materials, related to mass production of fuel cells. Thermoplastic/carbon filler composites with low filler loading have a major advantage in that they can be produced by a conventional low-cost injection molding technique. In addition, the materials used are inexpensive, easy to shape, and lightweight. An optimal bipolar plate must possess high surface and bulk electronic conductivity, sufficient mechanical integrity, low permeability, and corrosion resistance. However, it is difficult to achieve high electrical conductivity from a low-cost thermoplastic composite with low conductive filler loading. Concerns over electrical conductivity improvement and the injection processability of composites have brought forth the idea of producing a polypropylene/three-carbon-filler composite for bipolar plate application. The thesis addresses the development of synergistic effects of filler combinations, investigating composite conductive materials and using composite bipolar plate testing in PEMFCs. One significant effect of conductive network formation is the synergetic effects of different carbon filler sizes, shapes, and multiple filler ratios on the electrical conductivity of bipolar plate materials. A polypropylene resin combined with low-cost conductive fillers (graphite, conductive carbon black, and carbon fibers with 55 wt% of filler loading) compose the main composite for all investigations in this research. Numerous composite formulations, based on single-, two-, and three-filler systems, have been created to investigate the characteristics and synergistic effects of multiple fillers on composite conductivity. Electrical conductivity measurements corresponding to PEMFC performance and processing characteristics were investigated. Experimental work also involved other ex-situ testing for the physical requirements of commercial bipolar plates. All combinations of fillers were found to have a significant synergistic effect that increased the composite electrical conductivity. Carbon black was found to have the highest influence on the increase of electrical conductivity compared to the other fillers. The use of conjugated conducting polymers such as polypyrrole (PPy) to help the composite blends gain desirable conductivities was also studied. Electrical conductivity was significantly improved conductivity by enriching the conducting paths on the interfaces between fillers and the PP matrix with PPy. The conductive network was found to have a linkage of carbon fibers following the respective size distributions of fibers. The combination of Fortafil and Asbury carbon fiber mixture ameliorated the structure of conductive paths, especially in the through-plane direction. However, using small fibers such as carbon nanofibers did not significantly improve in electrical conductivity. The useful characteristics of an individual filler and filler supportive functions were combined to create a novel formula that significantly improved electrical conductivity. Other properties, such as mechanical and rheological ones, demonstrate the potential to use the composites in bipolar plate applications. This research contributes a direction for further improvement of marketable thermoplastic bipolar plate composite materials.

<p>In this work characterisation methods and fuel cell hardwarewere developed for studying the components of the polymerelectrolyte fuel cell (PEFC). Humidifiers and other componentswere tested in order to develop reproducible and reliableexperimental techniques. A set-up for testing larger cells andstacks was developed.</p><p>A new type of polymer electrolyte membrane fuel cell wasdeveloped for laboratory investigations. Current collectormaterial and gas flow channels can easily be modified in thisconstruction. The electrode potentials can be measured at thegas backing layers, thereby allowing measurement of contactresistances. The use of a reference electrode is alsopossible.</p><p>Contact resistances were studied in situ as a function oftime, clamping pressure, gas pressure and current density.Ex-situ measurements were used to validate the in-situ contactresistance measurements. The validity and error sources of theapplied in-situ measurement methods with reference electrodesand potential probes were studied using both computersimulations and experiments.</p><p>An in-house membrane electrode assembly (MEA) productionline was developed. In-house produced MEAs were utilised inboth membrane degradation and mass transport studies.</p><p>The durability testing of PVDF based membranes membranes wasstudied both by fuel cell experiments and ex-situ testing.Raman spectra were measured for used membranes.</p><p>A current distribution measurement method was developed. Theeffect of inlet humidification and gas composition at thecathode side was studied. In addition, two different flow fieldgeometries were studied. The results of current distributionmeasurements were used to validate a PEFC model.</p><p>Methods for characterising gas diffusion layer (GDL)performance by fuel cell testing and ex-situ measurements weredeveloped. The performance of GDL materials was tested withvarying cell compression and cathode humidity. Porosity, poresize distribution and contact angle were determined. Electricalcontact resistance, thermal impedance and gas permeabilitieswere measured at different compression levels.</p><p>Development work on a stack with stainless steel net wascarried out as well as characterisation studies of differentstack components. Thermal impedances and flow fieldpermeability were measured.</p><p>Mass transport limitations in the cathodes were studied byvarying the electrode thickness, partial pressure and humidityof oxygen.</p><p><b>Keywords:</b>polymer electrolyte membrane fuel cell (PEFC),contact resistance, clamping pressure, stainless steel,membrane degradation, current distribution, gas diffusionlayer, stack, thermal impedance, permeability.</p>

Polymer electrolyte membrane fuel cells (PEMFCs) have the potential to play a major role as energy generators for transportation and portable applications. One of the current barriers to their commercialization is the cost of the components and manufacturing, specifically the bipolar plates. One approach to preparing PEMFCs for commercialization is to develop new bipolar plate materials, related to mass production of fuel cells. Thermoplastic/carbon filler composites with low filler loading have a major advantage in that they can be produced by a conventional low-cost injection molding technique. In addition, the materials used are inexpensive, easy to shape, and lightweight. An optimal bipolar plate must possess high surface and bulk electronic conductivity, sufficient mechanical integrity, low permeability, and corrosion resistance. However, it is difficult to achieve high electrical conductivity from a low-cost thermoplastic composite with low conductive filler loading. Concerns over electrical conductivity improvement and the injection processability of composites have brought forth the idea of producing a polypropylene/three-carbon-filler composite for bipolar plate application. The thesis addresses the development of synergistic effects of filler combinations, investigating composite conductive materials and using composite bipolar plate testing in PEMFCs. One significant effect of conductive network formation is the synergetic effects of different carbon filler sizes, shapes, and multiple filler ratios on the electrical conductivity of bipolar plate materials. A polypropylene resin combined with low-cost conductive fillers (graphite, conductive carbon black, and carbon fibers with 55 wt% of filler loading) compose the main composite for all investigations in this research. Numerous composite formulations, based on single-, two-, and three-filler systems, have been created to investigate the characteristics and synergistic effects of multiple fillers on composite conductivity. Electrical conductivity measurements corresponding to PEMFC performance and processing characteristics were investigated. Experimental work also involved other ex-situ testing for the physical requirements of commercial bipolar plates. All combinations of fillers were found to have a significant synergistic effect that increased the composite electrical conductivity. Carbon black was found to have the highest influence on the increase of electrical conductivity compared to the other fillers. The use of conjugated conducting polymers such as polypyrrole (PPy) to help the composite blends gain desirable conductivities was also studied. Electrical conductivity was significantly improved conductivity by enriching the conducting paths on the interfaces between fillers and the PP matrix with PPy. The conductive network was found to have a linkage of carbon fibers following the respective size distributions of fibers. The combination of Fortafil and Asbury carbon fiber mixture ameliorated the structure of conductive paths, especially in the through-plane direction. However, using small fibers such as carbon nanofibers did not significantly improve in electrical conductivity. The useful characteristics of an individual filler and filler supportive functions were combined to create a novel formula that significantly improved electrical conductivity. Other properties, such as mechanical and rheological ones, demonstrate the potential to use the composites in bipolar plate applications. This research contributes a direction for further improvement of marketable thermoplastic bipolar plate composite materials.