Fractal model for prediction of effective thermal conductivity of gas diffusion layer in proton exchange membrane fuel cell

The process of heat transfer within porous media is usually considered as a transport through large numbers of straight channels with uniform pore sizes. For the prediction of effective thermal conductivity of gas diffusion layer (GDL), morphological properties such as the tortuosity of channels and pore-size distribution of this porous layer should be considered. Thus in this article, novel parallel and series-parallel prediction models of effective thermal conductivity for the GDL in proton exchange membrane fuel cell (PEMFC) have been derived by fractal theoretical characterization of the real microstructure of GDL. The prediction of fractal parallel model for carbon paper, a basal material of the GDL, is in good agreement with the reference value supplied by Toray Inc. The prediction results from the proposed models are also reasonable because they are distributed between the upper and lower bounds. Parametric effect has been investigated by using the presented models in dimensionless formalism. It can be concluded that dimensionless effective thermal conductivity (k^′eff${k^{\prime }}_{\text{eff}}$) has a positive correlation with effective porosity (?) or the pore-area fractal dimension (D_p) when k_s/k_g < 1; whereas it has a negative correlation with ? or D_p when k_s/k_g > 1 and with tortuous fractal dimension (D_t) whether k_s/k_g < 1 or not. Furthermore, these fractal models have been modified by considering the effect of polytetrafluoroethylene (PTFE) incorporated into the pore spaces of carbon paper, and the corresponding model prediction shows that there is an increase in the effective thermal conductivity due to the filling of PTFE that has high thermal conductivity.     

Highly conductive epoxy/graphite composites for bipolar plates in proton exchange membrane fuel cells

Carbon-filled epoxy composites are developed for potential application as bipolar plates in proton exchange membrane (PEM) fuel cells. These composites are prepared by solution intercalation mixing, followed by compression molding and curing. Electrical conductivity, thermal and mechanical properties, and hygrothermal characteristics are determined as function of carbon-filler content. Expanded graphite and carbon black are used as synergistic combination to obtain desired in-plane and through-plane conductivities. These composites show high glass transition temperatures (T_g ∼ 180 °C), high thermal degradation temperatures (T₂ ∼ 415 °C), in-plane conductivity of 200–500 S cm⁻¹ with 50 wt% carbon fillers, in addition to offering high values of flexural modulus, flexural strength, and impact strength, respectively 2 × 10⁴ MPa, 72 MPa, and 173 J m⁻¹. The presence of carbon fillers helps reduce water uptake from 4 to 5 wt% for unfilled epoxy resins to 1–2 wt%. In addition, morphology, electrical, mechanical, and thermal properties remain unchanged on exposure to boiling water and acid reflux. This data indicate that the composites developed in this work meet many attributes of bipolar plates for use in PEM fuel cells.     

Measurement of the through-plane thermal conductivity of carbon paper diffusion media for the temperature range from −50 to +120 °C

Carbon paper, a fibrous material, is often used as the gas diffusion layer in polymer electrolyte membrane (PEM) fuel cells, which are being vigorously developed as a zero-emission power source for transportation applications. The temperature field and heat transfer in this material is determined by its thermal conductivity and diffusivity, which are directly dependent on the operating temperature. In this work, we use a quasi-steady method known as the thermal capacitance (slug) method to experimentally measure the through-plane thermal conductivity of TORAY carbon paper for a temperature range from −50 to +120 °C. The effects of compression and PTFE loading on the overall thermal conductivity are also investigated. Compression leads to a decrease in thermal resistance between the carbon fibers; hence, an increase in the overall thermal conductivity. However, it is also found that this thermal resistance is highly dependent on the temperature and the PTFE loading. In contrast with our in-plane thermal conductivity measurements from a previous study, the through-plane thermal conductivity is found to increase with an increase in temperature in this study. This finding suggests that the thermal expansion of the carbon fibers is a direction dependent quantity.     

Study on the mesocarbon microbeads/polyphenylene sulfide composite bipolar plates applied for proton exchange membrane fuel cells

Thermoplastic/graphite composite bipolar plates based on polyphenylene sulfide (PPS) and mesocarbon microbeads (MCMB) were prepared by compression molding at a pressure of 40 MPa and 400 °C. Electrical conductivity, bulk density, flexural strength, water and ethanol absorption were determined as function of PPS content. The influences of molding time, actived carbon and carbon fiber on the properties of the composite bipolar plates were investigated, the cross section of the composite plates were analyzed by scanning electron microscope (SEM). We found that the optimized PPS content is 20 wt% and the required molding time is 30 min. In particular, the composite plates containing 20 wt% PPS demonstrated in-plane conductivity as high as 133.7 S cm⁻¹, through-plane conductivity 21.37 S cm⁻¹, in addition to showing the value of density, flexural strength, water and ethanol absorption as 1.98 g cm⁻³, 38.82 MPa, 0.0409 and 0.352 g cm⁻³. The addition of actived carbon degraded all the performance of the bipolar plate, while addition of carbon fiber improved almost all the performance of bipolar plate except bulk density and through-plane conductivity. The performances of fuel cell with this composite bipolar plate were tested, no distinct variation occurred after the composite plates operating in fuel cell. These data indicates the chemical and mechanical stability of the composite plates and their potential application in fuel cell.     

Effect of the anisotropic thermal conductivity of GDL on the performance of PEM fuel cells

Gas diffusion layers (GDLs) are one of the main components in proton exchange membrane (PEM) fuel cells. In this paper, the effect of anisotropic thermal conductivity of the GDL is numerically investigated under different operating temperatures. Furthermore, the sensitivity of the PEM fuel cell performance to the thermal conductivity of the GDL is investigated for both in-plane and through-plane directions and the temperature distributions between the different GDL thermal conductivities are compared. The results show that increasing the in-plane and through-plane thermal conductivity of the GDL increases the power density of PEM fuel cells significantly. Moreover, the temperature gradients show a greater sensitivity to the in-plane thermal conductivity of the GDL as opposed to the through-plane thermal conductivity.     

Characterization of transport properties in gas diffusion layers for proton exchange membrane fuel cells: 2. Absolute permeability

This is the second in a series of papers in which we present methods demonstrated in our group for the estimation of transport properties in gas diffusion layers (GDLs) for proton exchange membrane fuel cells (PEMFCs). Here we describe a method for determining separately the in-plane (x, y-directions) and through-plane (z-direction), viscous and inertial permeability coefficients of macro-porous substrates and micro-porous layers by controlling the direction of the gas flow through the porous sample. The method is applied initially to the macro-porous substrate of the GDL alone and subsequently to the macro-porous substrate with different micro-porous layers applied on it. The permeability coefficients of the micro-porous layer are calculated from the two measurements. The permeability coefficients are calculated from the Darcy–Forchheimer equation by application of the method of least squares. The method was applied to GDLs having different contents of polytetrafluoroethylene (PTFE) and carbon types. The samples with a higher PTFE content have in-plane and through-plane viscous permeability coefficients higher than those of the samples with lower PTFE content. The in-plane and through-plane viscous permeability coefficients also depend on the carbon type.     

Development of bipolar plates for fuel cells from graphite filled wet-lay material and a thermoplastic laminate skin layer

In this paper, a method with the potential to rapidly produce thermoplastic polymer composite bipolar plates with improved formability and through-plane conductivity is described. In our earlier work, it was reported that composite bipolar plates made with graphite filled wet-lay materials exhibited excellent mechanical properties and in-plane electrical conductivity. However, the through-plane conductivity and formability of the materials needed improvement. In this work, laminate polymer composite plates consisting of a wet-lay based core and a fluoropolymer/graphite skin layer are manufactured in an effort to improve formability and through-plane conductivity. These plates are characterized by their through-plane and in-plane conductivity, half-cell resistance, and mechanical properties at ambient and elevated temperatures. The laminate plates with PPS based wet-lay core exhibited bulk conductivities of above 300 S cm⁻¹, tensile strength of up to 34 MPa, and flexural strength of up to 54 MPa. Compared to the bipolar plates consisting of wet-lay material only, the bipolar plates with laminate structure exhibited an increase in through-plane conductivity of 25–35%, as well as a decrease in half-cell resistance by a factor of up to 5. The laminate bipolar plates can be manufactured in several ways with two of them being discussed in detail in the paper.     

Measurement of in-plane thermal conductivity of carbon paper diffusion media in the temperature range of −20 °C to +120 °C

Carbon paper is commonly used as the gas diffusion layer (GDL) in polymer electrolyte membrane (PEM) fuel cells as it exhibits high chemical and mechanical durability. This diffusion medium is also anisotropic, which directly affects its transport properties and specifically the thermal conductivity. In this study, the in-plane thermal conductivity of the carbon paper GDL was determined using thermal diffusivity measurements for a temperature range from −20 to +120 °C and four Teflon loadings (0, 5, 20 and 50 wt.%). It is important to understand the effect of temperature on the thermal conductivity since PEM fuel cells are designed to operate under various temperatures depending on the application of use. Further, Teflon is used to change the hydrophobic properties of the carbon paper GDL with 20 wt.% as the most widely used percentage. In this study, the Teflon loadings were chosen to gain a comprehensive understanding of the thermal resistance due to Teflon. In this study, a quasi-steady method was used to measure the thermal properties of the carbon paper; hence, the phase transformation in the presence of PTFE was investigated. The thermal conductivity decreases with an increase in temperature for all samples. The addition of as little as 5 wt.% Teflon resulted in high thermal resistance decreasing the overall thermal conductivity of the sample. Further addition of Teflon did not have major effects on the thermal conductivity. For all treated samples, the thermal conductivity lies in the range of 10.1–14.7 W/mK. Finally, empirical relations for the thermal diffusivity and conductivity with temperature were deduced.     

Numerical modeling and experimental study of the influence of GDL properties on performance in a PEMFC

This work is to study the effect of properties of gas diffusion layer (GDL) on performance in a polymer electrolyte membrane fuel cell (PEMFC) by both numerical simulation and experiments. The 1-dimension numerical simulation using the mixture-phase model is developed to calculate polarization curve. We are able to estimate optimum GDL properties for cell performance from numerical simulation results. Various GDLs which have different properties are prepared to verify accuracy of the simulation results. The contact angle and gas permeability of GDLs are controlled by polytetrafluoroethylene (PTFE) content in micro-porous layers (MPLs). MPL slurry is prepared by homogeneous blending of carbon powder, PTFE suspension, isopropyl alcohol and glycerol. Then the slurry is coated on gas diffusion mediums (GDMs) surface with controlled thickness by blade coating method. Non-woven carbon papers which have different thicknesses of 200 μm and 380 μm are used as GDMs. The prepared GDLs are measured by surface morphology, contact angle, gas permeability and through-plane electrical resistance. Moreover, the GDLs are tested in a 25 cm² single cell at 70 °C in humidified H₂/air condition. The contact angle of GDL increases with increasing PTFE content in MPL. However, the gas permeability and through-plane electrical conductivity decrease with increasing PTFE content and thickness of GDM. These changes in properties of GDL greatly influence the cell performance. As a result, the best performance is obtained by GDL consists of 200 μm thick non-woven carbon paper as GDM and MPL contained 20 wt.% PTFE content.     

Effect of hydrophobic gas diffusion layers on the performance of the polymer exchange membrane fuel cell

This study uses fuel cell gas diffusion layers (GDLs) fabricated in the laboratory from carbon fiber cloth with different concentrations of hydrophobic agents in proton exchange membrane fuel cells (PEMFCs), and investigates the relationship between the hydrophobic agent content of the carbon fiber cloth and fuel cell performance.The paper examines the effect of hydrophobic agent content on GDL thickness, contact angle, air permeability, and surface and through-plane resistivity. Carbon fiber cloth is impregnated with hydrophobic agent concentrations of 0, 3, 5, 10, 30, and 50 wt%, and the resulting GDLs are subjected to performance tests. When the test piece area is 25 cm², the test temperature 80 °C, the gasket thickness 0.36 mm, and the hydrophobic agent content 5 wt%, a fuel cell using the GDL has a current density of 1430 mA cm⁻² at 0.3 V.     

Evaluation of a compression molded composite bipolar plate for direct methanol fuel cell

A polymer–graphite composite bipolar plate of direct methanol fuel cell (DMFC) was fabricated by a compression molding method. The electrical conductivity and electrochemical behavior of the composite material under DMFC operating conditions were evaluated. The results show that the composite bipolar plate has a good electrical conductivity. Moreover, the through-plane conductivity of the composite material is higher than the in-plane one, which is ascribed to the anisotropic property of the composite bipolar plate resulted from the compression molding process. Corrosion tests show that the stable current density is below 10 μA cm⁻² under both anode and cathode conditions of DMFC. The discharge test of the DMFC single cell also presents a satisfactory result.     

A three-dimensional analysis of the effect of anisotropic gas diffusion layer(GDL) thermal conductivity on the heat transfer and two-phase behavior in a proton exchange membrane fuel cell(PEMFC)

A three-dimensional and two-phase model was employed to investigate the effect of the anisotropic GDL thermal conductivity on the heat transfer and liquid water removal in the PEMFCs with serpentine flow field and semi-counter flow operation. The GDL with different anisotropic thermal conductivity in the three directions (x, y, z) was simulated for four cases. As a result, the water saturation, temperature, species, current, potential distribution and proton conductivity were obtained. According to the comparison between the results of each case, some new conclusions are obtained and listed as below: (1) The anisotropic GDL produces the high temperature difference than that of isotropic case, and the in-plane thermal conductivity perpendicular to the gas channels is more important than that of along channels, which may produce the larger temperature difference. (2) Water saturation decreases due to the large temperature difference in the anisotropic case, but some water vapor may condense in the area neighbor to the channel ribs due to the cool function of the current collector and the great temperature difference. (3) The anisotropic thermal conductivity in the through-plane direction and the in-plane direction perpendicular to the gas channels can lead to the decrease of the membrane conductivity. (4) The isotropic GDL is better than that of anisotropic one for the uniform current density. Also, in-plane thermal conductivity perpendicular to the channels has more negative effect on the current density distribution in the membrane than that of the along channels one.     

Through-plane thermal conductivity of the microporous layer in a polymer electrolyte membrane fuel cell

Understanding the thermal properties of the microporous layer (MPL) is critical for accurate thermal analysis and improving the performance of proton exchange membrane (PEM) fuel cells operating at high current densities. In this study, the effective through-plane thermal conductivity and contact resistance of the MPL have been investigated. Gas diffusion layer (GDL) samples, coated with 5%-wt. PTFE, with and without an MPL are measured using the guarded steady-state heat flow technique described in the ASTM standard E 1225-04. Thermal contact resistance of the MPL with the iron clamping surface was found to be negligible, owing to the high surface contact area. Effective thermal conductivity and thickness of the MPL remained constant for compression pressures up to 15 bar at 0.30 W/m°K and 55 μm, respectively. The effective thermal conductivity of the GDL substrate containing 5%-wt. PTFE varied from 0.30 to 0.56 W/m°K as compression was increased from 4 to 15 bar. As a result, GDL containing MPL had a lower effective thermal conductivity at high compression than the GDL without MPL. At low compression, differences were negligible. The constant thickness of the MPL suggests that the porosity, as well as heat and mass transport properties, remain independent of the inhomogeneous compression by the bipolar plate. Despite the low effective thermal conductivity of the MPL, thermal performance of the GDL can be improved by exploiting the excellent surface contact resistance of the MPL.     

Semi-empirical modeling of electrical conductivity for composite bipolar plate with multiple reinforcements

Carbon composite bipolar plates were developed by compression molding of novolac type phenol formaldehyde resin with natural graphite, carbon black, and carbon fiber. The General Effective Media equation was adapted to model the electrical conductivity of the bipolar plate. The experimental values of the electrical conductivity of the composites with different reinforcements were well predicted by the model. For resin-graphite system (2-component), the most effective in-plane and through-plane electrical conductivities for 70% graphite content were found to be 201.26 and 40.91 S cm⁻¹, respectively. Similarly, for optimum resin-graphite-carbon black system (3-component), these values were found as 269.55 and 82.77 S cm⁻¹, respectively. The most effective in-plane and through-plane electrical conductivities were found to be 285.54 and 91.79 S cm⁻¹, respectively, for the composite with resin-graphite-carbon black-carbon fiber system (4-component). The predicted electrical conductivities for all the three systems were found to be in well agreement with the experimental values.     

Degradation of gas diffusion layers through repetitive freezing

This work investigates the degradation of an individual gas diffusion layer (GDL) by repeated freezing cycles. The pore size distribution, gas permeability, surface structure, and contact angle on the surface of the GDL were measured in four different types of GDL: SGL paper with a microporous layer (MPL); SGL paper with 5 wt% of polytetrafluoroethylene (PTFE) loading; Toray paper without PTFE loading; and Toray paper with 20 wt% of PTFE loading. After repeated freezing cycles, the porosity of the GDL without PTFE was reduced by 27.2% due to the volumetric expansion of the GDL. The peak of the log differential intrusion moved toward a smaller pore diameter slightly because of the repeated freezing process. The crack of the MPL increased in its width and length after repeated freezing cycles. The through-plane gas permeability of the GDL with the MPL doubled after repeated freezing cycles due to the growth of the crack in the MPL, but was very small for the GDLs with Toray paper. Besides, the GDLs with PTFE loading showed a relatively larger decrease in the contact angle on the surface than the GDL without PTFE loading due to the separation of PTFE from the carbon fiber during the repeated freezing process.     

Preparation and properties of thin epoxy/compressed expanded graphite composite bipolar plates for proton exchange membrane fuel cells

Although the composite bipolar plates prepared by the method of the vacuum resin impregnation in compressed expanded graphite (CEG) sheets have been applied in the KW-class stacks, there have been few investigations of the preparation and properties of them so far. In this research, the influences of the microstructure on the physical properties of the thin epoxy/CEG composites (the thickness is 1 mm) are investigated for the first time and the optimum preparation conditions are obtained. Results demonstrated that the mechanical property and the impermeability of the composites increases evidently with the resin content changing from 4% to 30%, while the electrical properties keep nearly constant. It can be attributed to the continuous expanded graphite (EG) conductive network of the raw CEG sheet. The epoxy (30 wt.%)/CEG composite is shown to be the optimum composite, displaying in-plane conductivity of 119.8 S cm⁻¹, through-plane resistance of 17.13 mΩ cm², density of 1.95 g cm⁻³, gas permeability of 1.94 × 10⁻⁶ cm³ cm⁻² s⁻¹ and flexural strength of 45.8 MPa. The alcohol scrubbing is the optimum method of surface post-processing. The performance of a single cell with the optimum composite bipolar plates is tested and demonstrated to be outstanding. Above all, the composite prepared by resin vacuum impregnation in the CEG sheet is a promising candidate for bipolar plate materials in PEMFCs.     

Electrical and thermal conductivities of novel metal mesh hybrid polymer composite bipolar plates for proton exchange membrane fuel cells

This study prepares novel metal mesh hybrid polymer composite bipolar plates for proton exchange membrane fuel cells (PEMFCs) via inserting a copper or aluminum mesh in polymer composites. The composition of polymer composites consists of 70 wt% graphite powder and 0-2 wt% modified multi-walled carbon nanotubes (m-MWCNTs). Results indicate that the in-plane electrical conductivity of m-MWCNTs/polymer composite bipolar plates increased from 156 S cm⁻¹ (0 wt% MWCNT) to 643 S cm⁻¹ (with 1 wt% MWCNT) (D.O.E. target >100 S cm⁻¹). The bulk thermal conductivities of the copper and aluminum mesh hybrid polymer composite bipolar plates (abbreviated to Cu-HPBP and Al-HPBP) increase from 27.2 W m⁻¹ K⁻¹ to 30.0 W m⁻¹ K⁻¹ and 30.4 W m⁻¹ K⁻¹, respectively. The through-plane conductivities decrease from 37.8 S cm⁻¹ to 36.7 S cm⁻¹ for Cu-HPBP and 22.9 S cm⁻¹ for Al-HPBP. Furthermore, the current and power densities of a single fuel cell using copper or aluminum mesh hybrid polymer composite bipolar plates are more stable than that of using neat polymer composite bipolar plates, especially in the ohmic overpotential region of the polarization curves of single fuel cell tests. The overall performance confirms that the metal mesh hybrid polymer composite bipolar plates prepared in this study are promising for PEMFC application.     

The influence of anode gas diffusion layer on the performance of low-temperature DMFC

The influence of the anode gas diffusion layers (GDLs) on the performances of low-temperature DMFCs, and the properties of mass transport and CO₂ removal on these anode GDLs were investigated. The membrane electrode assembly (MEA) based on the hydrophilic anode GDL, which consisted of the untreated carbon paper and hydrophilic anode micro-porous layer (comprised carbon black and 10 wt.% Nafion), showed the highest power density of 13.4 mW cm⁻² at 30 °C and ambient pressure. The performances of the MEAs tended to decline with the increase of the PTFE content in the anode GDLs due to the difficulty of methanol transport. The contact angle measurements revealed that the wettabilities of the anode GDLs decreased as the increase of PTFE content. The wettabilities of the GDLs were improved by addition of hydrophilic Nafion ionomer to the GDLs. From the visualizations of CO₂ gas bubbles dynamics on the anodes using a transparent cell, it was observed that uniform CO₂ gas bubbles with smaller size formed on hydrophilic anode GDLs. And bubbles with larger size were not uniform over the hydrophobic anode GDLs. It was believed that adding PTFE to the anode GDL was not helpful for improving the CO₂ gas transport in the anode GDL of the low-temperature DMFC.     

The influence of gas diffusion layer wettability on direct methanol fuel cell performance: A combined local current distribution and high resolution neutron radiography study

The influence of the anode and cathode GDL wettability on the current and media distribution was studied using combined in situ high resolution neutron radiography and locally resolved current distribution measurements. MEAs were prepared by vertically splitting either the anode or cathode carbon cloth into a less hydrophobic part (untreated carbon cloth ‘as received’) and a more hydrophobic part (carbon cloth impregnated by PTFE dispersion). Both parts were placed side by side to obtain a complete electrode and hot-pressed with a Nafion membrane. MEAs with partitioned anode carbon cloth revealed no difference between the untreated and the hydrophobised part of the cell concerning the fluid and current distribution. The power generation of both parts was almost equal and the cell performance was similar to that of an undivided MEA (110 mW cm⁻², 300 mA cm⁻², 70 °C). In contrast, MEAs with partitioned cathode carbon cloth showed a better performance for the hydrophobised part, which contributed to about 60% of the overall power generation. This is explained by facilitated oxygen transport especially in the hydrophobised part of the cathode gas diffusion layer. At an average current density of 300 mA cm⁻², a pronounced flooding of the cathode flow field channels adjacent to the untreated part of GDL led to a further loss of performance in this part of the cell. The low power density of the untreated part caused a significant loss of cell performance, which amounted to less than 40 mW cm⁻² (at 300 mA cm⁻²).     

Stable,easily sintered Ca–Zn-doped YCrO3 as novel interconnect materials for co-fired yttrium-stabilized zirconia-based solid oxide fuel cells

In order to develop co-fired yttrium-stabilized zirconia (YSZ)-based solid oxide fuel cells (SOFCs), stable and easily sintered Y_0.7Ca_0.3Cr_1−xZn_xO_3−δ (x = 0–0.15) perovskite oxides were synthesized by the microwave-aided sol–gel process and then examined as novel ceramic interconnect materials. (The characterizations focused on phase structure, sintering behavior, relative density, electrical conductivity and thermal expansion.) The XRD analysis indicates that a pure orthorhombic perovskite phase was obtained for all the samples. Cell volume decreases as x increases from 0 to 0.10. The Y_0.7Ca_0.3Cr_0.9Zn_0.1O_3–δ (YCCZ10) powder exhibited the best sintering ability, and a relative density of 96.6% could be obtained for the sample sintered at 1400 °C for 4 h in air. The electrical conductivities of the specimens increase with the Zn²⁺ content at x ≤ 0.10, but then remarkably decrease at x = 0.15, which might relate to the over-range of the substitution amount of Zn (0.15) for Cr position. YCCZ10 shows a remarkable electrical conductivity of 20.9 S cm⁻¹ at 850 °C in air, and a very suitable thermal expansion coefficient value of 10.8 × 10⁻⁶ K⁻¹ (YSZ: ∼10.8 × 10⁻⁶ K⁻¹). These investigations have indicated that YCCZ10 is a promising interconnect material for co-fired YSZ-based SOFCs.