A graphite-coated carbon fiber epoxy composite bipolar plate for polymer electrolyte membrane fuel cell

A PEMFC (polymer electrolyte membrane fuel cell or proton exchange membrane fuel cell) stack is composed of GDLs (gas diffusion layers), MEAs (membrane electrode assemblies), and bipolar plates. One of the important functions of bipolar plates is to collect and conduct the current from cell to cell, which requires low electrical bulk and interfacial resistances. For a carbon fiber epoxy composite bipolar plate, the interfacial resistance is usually much larger than the bulk resistance due to the resin-rich layer on the composite surface.In this study, a thin graphite layer is coated on the carbon/epoxy composite bipolar plate to decrease the interfacial contact resistance between the bipolar plate and the GDL. The total electrical resistance in the through-thickness direction of the bipolar plate is measured with respect to the thickness of the graphite coating layer, and the ratio of the bulk resistance to the interfacial contact resistance is estimated using the measured data. From the experiment, it is found that the graphite coating on the carbon/epoxy composite bipolar plate has 10% and 4% of the total electrical and interfacial contact resistances of the conventional carbon/epoxy composite bipolar plate, respectively, when the graphite coating thickness is 50 μm.     

Electromagnetic-carbon surface treatment of composite bipolar plate for high-efficiency polymer electrolyte membrane fuel cells

Polymer electrolyte membrane (PEM) or proton-exchange membrane fuel cell systems are environmentally friendly power sources for many applications. Bipolar plates are essential components of a PEM fuel cell. Recently, composite bipolar plates have received considerable interest due to their superior performance. The most important properties of bipolar plates are electrical resistance and contact resistance, which are largely dependent on the surface morphology of the bipolar plate, because low electrical resistance improves the efficiency of PEM fuel cells. In this study, a selective surface preparation technology is developed using an electromagnetic field and carbon black (electromagnetic-carbon surface treatment). The carbon black is heated by an electromagnetic field on the surface of the bipolar plate with a high rate of temperature rise. The non-electrically conducting surface resin is removed, without damaging the carbon fibre to give a low electrical resistance. It is found that the surface-treated composite bipolar plate has a lower electrical resistance than those of conventional composite bipolar plates, and that the electromagnetic-carbon surface treatment can be applied for production of the composite bipolar plates in a fast and efficient process.     

Bipolar plates made of plain weave carbon/epoxy composite for proton exchange membrane fuel cell

Polymer electrolyte membrane fuel cell or proton exchange membrane fuel cell (PEMFC) is composed of bipolar plates, end plates, membrane electrode assemblies (MEAs) and gas diffusion layers (GDLs). Among the constituents of PEMFCs, the bipolar plate is a key component that collects and conducts the current from cell to cell. The electrical resistance of the bipolar plate, which consists of the bulk material resistance and interfacial contact resistance between the GDLs and the bipolar plates, should be reduced to improve the performance of the fuel cell.     

Evaluation of coated metallic bipolar plates for polymer electrolyte membrane fuel cells

Metallic bipolar plates for polymer electrolyte membrane (PEM) fuel cells typically require coatings for corrosion protection. Other requirements for the corrosion protective coatings include low electrical contact resistance, good mechanical robustness, low material and fabrication cost. The authors have evaluated a number of protective coatings deposited on stainless steel substrates by electroplating and physical vapor deposition (PVD) methods. The coatings are screened with an electrochemical polarization test for corrosion resistance; then the contact resistance test was performed on selected coatings. The coating investigated include Gold with various thicknesses (2 nm, 10 nm, and 1 μm), Titanium, Zirconium, Zirconium Nitride (ZrN), Zirconium Niobium (ZrNb), and Zirconium Nitride with a Gold top layer (ZrNAu). The substrates include three types of stainless steel: 304, 310, and 316. The results show that Zr-coated samples satisfy the DOE target for corrosion resistance at both anode and cathode sides in typical PEM fuel cell environments in the short-term, but they do not meet the DOE contact resistance goal. Very thin gold coating (2 nm) can significantly decrease the electrical contact resistance, however a relatively thick gold coating (>10 nm) with our deposition method is necessary for adequate corrosion resistance, particularly for the cathode side of the bipolar plate.     

Investigation on the corrosion resistance of carbon black-graphite-poly(vinylidene fluoride) composite bipolar plates for polymer electrolyte membrane fuel cells

The goal of the present work was to evaluate the corrosion resistance of carbon black (CB)-synthetic graphite (SG)-poly(vinylidene fluoride) (PVDF) composites using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves. The tests were conducted in 0.5 M H₂SO₄ + 2 ppm HF solution at 70 °C to simulate the typical environment of polymer electrolyte membrane fuel cells. The fracture surface of the specimens was characterized by scanning electron microscopy. The through-plane electrical conductivity was also determined. The corrosion resistance decreased as the carbon black content increased up to 5 wt.%. The highest electrical conductivity was achieved for the composition CB = 5 wt.%, PVDF = 15 wt.%, SG = 80 wt.%. A detailed discussion of the EIS data is given. This approach is unprecedented in the current literature. EIS has proven to be a valuable tool to the design of electrically efficient bipolar plates.     

Conductivity of Nafion 117 membrane used in polymer electrolyte fuel cells

The membrane electric transport (MC) directly influences the performance of the polymer electrolyte fuel cells (PEMFC). The membrane conductivity is determined by a number of parameters such as: hydration technique, graphite cell geometry and pressure applied when the membrane electrode assembly (MEA) is joined. In addition, the membrane conductivity might be influenced by the electrode position due to the possibility of anisotropic electric conductivity.     

Ex situ evaluation of nanometer range gold coating on stainless steel substrate for automotive polymer electrolyte membrane fuel cell bipolar plate

The bipolar plate in polymer electrolyte membrane (PEM) fuel cell helps to feed reactant gases to the membrane electrode assembly (MEA) and collect current from the MEA. To facilitate these functions, the bipolar plate material should exhibit excellent electrical conductivity and corrosion resistance under fuel cell operating conditions, and simultaneously be of low-cost to meet commercialization enabling targets for automotive fuel cells. In the present work, we focus on the benchmarking of 10 nm gold coated SS316L (a.k.a. Au Nanoclad^®) bipolar plate material through ex situ tests, which is provided by Daido Steel (Japan). The use of nanometer range Au coatings help to retain the noble properties of gold while significantly reducing the cost of the bipolar plate. The area specific resistance of the flat sample is 0.9 mΩ cm² while that for the formed bipolar plate is 6.3 mΩ cm² at compaction force of 60 N cm⁻². The corrosion current density was less than 1 μA cm⁻² at 0.8 V/NHE with air sparge simulating cathodic conditions. Additionally, gold coated SS316L showed anodic passivation of SS316L, thereby exhibiting robustness towards coating defects including surface scratches that may originate during the manufacturing of the bipolar plate. These series of ex situ tests indicate that 10 nm gold coated SS316L has good potential to be considered for commercial bipolar plates in automotive fuel cell stack.     

A novel cesium hydrogen sulfate-zeolite inorganic composite electrolyte membrane for polymer electrolyte membrane fuel cell application

A new type of CsHSO₄-HZSM-5 inorganic composite electrolyte membrane is prepared by mechanically mixing CsHSO₄ (CHS) and nanometer-scale HZSM-5 zeolite powders. The effects of HZSM-5 on the crystallite structure, proton conductivity, and thermal stability of the CsHSO₄ electrolyte are investigated. Incorporation of HZSM-5 is found to significantly increase the low-temperature proton conductivity of the CsHSO₄ electrolyte, extending its operating temperature down to 100 °C. The composite electrolyte with 40 mol% HZSM-5 shows the highest proton conductivity in the measured temperature range. The low-temperature activation energy of the composite with 40 mol% HZSM-5 is lower than that of the CHS-SiO₂ composite. The improvement of the proton conductivity can be attributed to the enhanced interfacial interaction between the two phases. And the small HZSM-5 particles lead to a change in the bulk properties of the ionic salts. The melting point of the CHS-HZSM-5 composite electrolyte is lower than that of the pure CHS electrolyte. The CHS-HZSM-5 composite electrolyte is suitable for polymer electrolyte membrane fuel cells operated at 100-200 °C.     

Effect of graphite sizes and carbon nanotubes content on flowability of bulk-molding compound and formability of the composite bipolar plate for fuel cell

This study investigates the flowability of the bulk-molding compound (BMC) on composite bipolar plates containing graphite content from 70 to 80 wt% with different graphite sizes. A small quantity (from 0.25 to 2 wt%) of multi-walled carbon nanotubes (MWCNT) is also added. Findings show that the flowability of BMC material decreases with decreasing graphite size and with increasing graphite content. The BMC material containing large size graphite (177-125 μm) entirely exhibits a relatively higher flowability within the analysis graphite contents, in the range of 73.3-11.3 cm, compared to the small size (74-45 μm), in which flowability is in the range of 40.3-6.67 cm. Further adding MWCNT causes decreased flowability of the BMC material especially when the percolated networking structure is formed through the resin. Therefore, with flowability below 10 cm, the formability of a large area (300 mm × 300 mm × 3 mm) or thin (100 mm × 100 mm × 0.5 mm) composite bipolar plate shows a large area of surface porosity or visible defects. Results indicate that the flowability of the thermoset-based BMC material is an important design parameter to fabricate cost-effective, large, or thin composite bipolar plates.     

Novel functionalized carbon nanotubes as cross-links reinforced vinyl ester/nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

In this study, the novel functionalized multi-walled carbon nanotubes (MWCNTs) are used as cross-links between MWCNTs-vinyl ester interfaces to achieve homogeneous dispersion and strong interfacial bonding for developing fully integrated MWCNTs-vinyl ester nanocomposite bipolar plates. POAMA (i.e. poly(oxyalkylene)-amines (POA) bearing maleic anhydride (MA)) are grafted onto the MWCNTs by amidization reaction, forming MWCNTs-POAMA. In the MWCNTs-POAMA/vinyl ester nanocomposites, MWCNT-POAMAs react with vinyl ester and become part of the cross-linked structure, rather than just a separate component. It is found that the MWCNTs-POAMA exhibited better dispersion in the vinyl ester matrix than those of pristine MWCNTs. Moreover, the results demonstrate that the mechanical and electrical properties of the vinyl ester nanocomposite bipolar plate are improved dramatically. The ultimate flexural strength, unnotched impact strength, in-plane electrical conductivity and contact resistance of the MWCNTs-POAMA/vinyl ester nanocomposite bipolar plate are increased by 45%, 90%, 315% and 28%, respectively. In addition, the maximum current and power densities of the single fuel cell test using the MWCNTs-POAMA/vinyl ester nanocomposite bipolar plates is enhanced from 1.03 to 1.23 A cm⁻² and from 0.366 to 0.518 W cm⁻², respectively, which suggested that a higher electron transfer ability for polymer electrolyte membrane fuel cell applications can be achieved.     

The preparation technique optimization of epoxy/compressed expanded graphite composite bipolar plates for proton exchange membrane fuel cells

Vacuum resin impregnation method has been used to prepare polymer/compressed expanded graphite (CEG) composite bipolar plates for proton exchange membrane fuel cells (PEMFCs). In this research, three different preparation techniques of the epoxy/CEG composite bipolar plate (Compression-Impregnation method, Impregnation-Compression method and Compression-Impregnation-Compression method) are optimized by the physical properties of the composite bipolar plates. The optimum conditions and the advantages/disadvantages of the different techniques are discussed respectively. Although having different characteristics, bipolar plates obtained by these three techniques can all meet the demands of PEMFC bipolar plates as long as the optimum conditions are selected. The Compression-Impregnation-Compression method is shown to be the optimum method because of the outstanding properties of the bipolar plates. Besides, the cell assembled with these optimum composite bipolar plates shows excellent stability after 200 h durability testing. Therefore the composite prepared by vacuum resin impregnation method is a promising candidate for bipolar plate materials in PEMFCs.     

Simulation of nanostructured electrodes for polymer electrolyte membrane fuel cells

Aligned carbon nanotubes (CNTs) with Pt uniformly deposited on them are being considered in fabricating the catalyst layer of polymer electrolyte membrane (PEM) fuel cell electrodes. When coated with a proton conducting polymer (e.g., Nafion) on the Pt/CNTs, each Pt/CNT acts as a nanoelectrode and a collection of such nanoelectrodes constitutes the proposed nanostructured electrodes. Computer modeling was performed for the cathode side, in which both multicomponent and Knudsen diffusion were taken into account. The effect of the nanoelectrode lengths was also studied with catalyst layer thicknesses of 2, 4, 6, and 10 μm. It was observed that shorter lengths produce better electrode performance due to lower diffusion barriers and better catalyst utilization. The effect of spacing between the nanoelectrodes was studied. Simulation results showed the need to have sufficiently large gas pores, i.e., large spacing, for good oxygen transport. However, this is at the cost of obtaining large electrode currents due to reduction of the number of nanoelectrodes per unit geometrical area of the nanostructured electrode. An optimization of the nanostructured electrodes was obtained when the spacing was at about 400 nm that produced the best limiting current density.     

Effect of carbon fillers on properties of polymer composite bipolar plates of fuel cells

Bipolar plates are major components of fuel cell (FC) stacks and they make up a large portion of the stack volume and cost. In order to reduce their weight and fabrication cost, polymer composite materials with various carbon conducting fillers are tested for use as composite bipolar plates for FCs. The composite materials are prepared by using graphite with a small vol.% of carbon black (CB), multi-walled carbon nanotubes (MWNTs) or carbon fibres (CF) in an epoxy resin. The electrical conductivity and flexural properties of the composites are measured as a function of the carbon conductive filler content. The highest electrical conductivity is observed at a total conducting filler content of 75 vol.%. The addition of a small amount of hybrid conducting filler enhances the electrical conductivity up to certain threshold, viz. 5 vol.% of CB, 2 vol.% of MWNTs, and 7 vol.% of CF. Above these thresholds, the electric conductivity decreases with increasing filler content, due to the lack of sufficient resin to bind the fillers tightly. The hybrid filler system has better properties than the single filler system. The experimental results indicate that there is an optimum composition range with respect to electrical conductivity and mechanical properties.     

Effect of surface wettability of polymer composite bipolar plates on polymer electrolyte membrane fuel cell performances

The effects of fluoropolymer based additive at different additive/binder and additive/filler ratios on surface wettability, conductivity and mechanical properties of polymer composite bipolar plates are investigated in this study. Fuel cell performance tests are performed at different feed flow rates by using composite bipolar plates containing organic based hydrophobic and inorganic based hydrophilic additives to investigate the effect of surface wettability properties on polymer electrolyte membrane fuel cell (PEMFC) performance. The conductivity of the composite materials decreases with the increase in additive/filler ratios, due to a decrease in the amount of conductive filler in the composite structure, whereas conductivity increases with the increase in additive/binder ratios due to a decrease in the amount of nonconductive binder. The surface hydrophobicity gets stronger with increasing fluoropolymer/filler and fluoropolymer/binder ratio amounts, related to the hydrophobic properties of both filler and fluoropolymer. In all feed flow rates, at low current densities, the single cells exhibit almost the same performance. At intermediate and high current densities, polymer composite without any additives shows higher performance than the bipolar plates containing organic or inorganic based additives. Current and power densities show maxima at the bipolar plate contact angle of 80°.     

New materials for polymer electrolyte membrane fuel cell current collectors

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.     

Preparation and properties of carbon nanotube/polypropylene nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

This study aims at the fabrication of lightweight and high performance nanocomposite bipolar plates for the application in polymer electrode membrane fuel cells (PEMFCs). The thin nanocomposite bipolar plates (the thickness <1.2 mm) consisting of multiwalled carbon nanotubes (MWCNTs), graphite powder and PP were fabricated by means of compression molding. Three types of polypropylene (PP) with different crystallinities including high crystallinity PP (HC-PP), medium crystallinity PP (MC-PP), low crystallinity PP (LC-PP) were prepared to investigate the influence of crystallinity on the dispersion of MWCNTs in PP matrix. The optimum composition of original composite bipolar plates was determined at 80 wt.% graphite content and 20 wt.% PP content based on the measurements of electrical and mechanical properties with various graphite contents. Results also indicate that MWCNTs was dispersed better in LC-PP than other PP owing to enough dispersed regions in nanocomposite bipolar plates. This good MWCNT dispersion of LC-PP would cause better bulk electrical conductivity, mechanical properties and thermal stability of MWCNTs/PP nanocomposite bipolar plates. In the MWCNTs/LC-PP system, the bulk electrical conductivities with various MWCNT contents all exceed 100 S cm⁻¹. The flexural strength of the MWCNTs/LC-PP nanocomposite bipolar plate with 8 phr of MWCNTs was approximately 37% higher than that of the original nanocomposite bipolar plate and the unnotched Izod impact strength of MWCNTs/LC-PP nanocomposite bipolar plates was also increased from 68.32 J m⁻¹ (0 phr) to 81.40 J m⁻¹ (8 phr), increasing 19%. In addition, the coefficient of thermal expansion of MWCNTs/LC-PP nanocomposite bipolar plate was decreased from 32.91 μm m⁻¹ °C⁻¹ (0 phr) to 25.79 μm m⁻¹ °C⁻¹ (8 phr) with the increasing of MWCNT content. The polarization curve of MWCNTs/LC-PP nanocomposite bipolar plate compared with graphite bipolar plate was also evaluated. These results confirm that the addition of MWCNTs in LC-PP leads to a significant improvement on the cell performance of the nanocomposite bipolar plate.     

The inhibition of electrochemical carbon corrosion in polymer electrolyte membrane fuel cells using iridium nanodendrites

The addition of Ir-based water electrolysis catalysts to the catalyst layer in polymer electrolyte membrane fuel cells was examined as a promising approach for preventing electrochemical carbon corrosion under severely corrosive conditions. Electrochemical carbon corrosion of membrane electrode assemblies containing different amounts of IrO₂ or shape-controlled Ir dendrite catalysts were characterized using on-line mass spectrometry. In particular, Ir dendrite catalysts possess high activity toward oxygen evolution reactions when compared to IrO₂. As a result, Ir dendrites provided a very effective method of removing water from the catalyst layer. Therefore, the addition of 1 wt% Ir dendrite (0.008 mg cm⁻²) to the catalyst layer of the cathode decreased electrochemical carbon corrosion by 84% at 1.6 V_NHE compared with a conventional membrane electrode assembly in the absence of water electrolysis catalysts.     

Preparation and properties of functionalized multiwalled carbon nanotubes/polypropylene nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

Multiwalled carbon nanotubes (MWCNTs) are covalently modified with different molecular weights 400 and 2000 poly(oxyalkylene)-amine bearing the diglycidyl ether of bisphenol A (DGEBA) epoxy (POA400-DGEBA and POA2000-DGEBA) oligomers. The oxidized MWCNTs (MWCNTs-COOH) are converted to the acid chloride-functionalized MWCNTs, followed by the reaction with POA-DGEBAs to prepare the MWCNTs/POA400-DGEBA and MWCNTs/POA2000-DGEBA. FTIR, thermogravimetric analysis (TGA) and high resolution X-ray photoelectron spectra (XPS) reveal that the POA-DGEBAs are covalently attached to the surface of MWCNTs. The morphology of MWCNTs/POA-DGEBA is observed by TEM. The POA400-DGEBA coated on the MWCNTs is thicker and more uniform. However, the coating of POA2000-DGEBA on the MWCNTs shows a worm-like bulk substance and the MWCNT surface is bare. In addition, the flexural strength and the bulk electrical conductivity of the MWCNTs/polypropylene nanocomposite bipolar plates are measured 59% and 505% higher than those of the original composite bipolar plates by adding 8 phr of MWCNTs/POA400-DGEBA. The maximum current density and power density of the single cell test for the nanocomposite bipolar plate with 4 phr MWCNTs/POA400-DGEBA are 1.32 A cm⁻² and 0.533 W cm⁻², respectively. The overall performance confirms the functionalized MWCNTs/polypropylene nanocomposite bipolar plates prepared in this study are suitable for PEMFC application.     

Carbon materials in composite bipolar plates for polymer electrolyte membrane fuel cells: A review of the main challenges to improve electrical performance

The technology of polymer electrolyte membrane (PEM) fuel cells is dependent on the performance of bipolar plates. There is a strong relationship between the material used in the manufacturing of the bipolar plate and its final properties. Graphite-polymer composite bipolar plates are well-established commercial products. Several other carbon based fillers are tested. Carbon nanotubes, carbon fibers, carbon black, graphite nanoplatelets and expanded graphite are examples of such materials. Structural characteristics of these particles such as morphology and size have decisive influence on the final properties of bipolar plates. Furthermore, the volumetric fraction of the filler is of prime importance. There is plenty of information on individual aspects of specific composite bipolar plates in the literature. Notwithstanding, the analysis of structure-property relationship of these materials in a comprehensive source is not found. In this paper, relevant topics on the structural aspects of carbon based fillers and how they influence the final electrical performance of composite bipolar plates are discussed. It is intended that this document contribute to the development of new and maximized products to the PEM fuel cell industry.     

Preparation and properties of carbon nanotube-reinforced vinyl ester/nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

Novel multiwalled carbon nanotubes (MWNTs) were prepared using poly(oxypropylene)-backboned diamines of molecular weights M_w 400 and 2000 to disperse acid-treated MWNTs, improving the performance of composite bipolar plates in polymer electrolyte membrane fuel cells. A lightweight polymer composite bipolar plate that contained vinyl ester resin, graphite powder and MWNTs was fabricated using a bulk molding compound (BMC) process. Results demonstrate that the qualitative dispersion of MWNTs crucially determined the resultant bulk electrical conductivity, the mechanical properties and the physical properties of bipolar plates. The flexural strength of the composite bipolar plate with 1 phr of MWNTs was approximately 48% higher than that of the original composite bipolar plate. The coefficient of thermal expansion of the composite bipolar plate was reduced from 37.00 to 20.40 μm m⁻¹ °C⁻¹ by adding 1 phr of MWNTs, suggesting that the composite bipolar plate has excellent thermal stability. The porosity of the composite bipolar plate was also evaluated. Additionally, the bulk electrical conductivity of the composite bipolar plate with different MWNTs types and contents exceeds 100 S cm⁻¹. The results of the polarization curves confirm that the addition of MWNTs leads to a significant improvement on the single cell performance.