Improved polymer electrolyte fuel cell performance with membrane electrode assemblies using modified metallic plate: Comparative study on impact of various coatings

Bipolar plate is one of the key components of polymer electrolyte membrane fuel cell. In the present study, metallic plates are explored as bipolar plates in comparison to most generally used high-density graphite plates. Among various metals, stainless steel 316L is preferred due to its low cost, high strength, ease of machining and for its corrosion resistance characteristics. However, the challenges associated with metallic plates are high interfacial contact resistance due to passive oxide layer formation and possible corrosion product during operation in chemically harsh environments, which may contaminate the membrane electrode assembly. Three electrically conductive and corrosion resistant coatings namely Titanium Nitrides, Plasma Nitride, and Gold have been coated over the surface of stainless steel 316L metallic plate to overcome these challenges and to explore their impact on fuel cell performance using standard membrane electrode assemblies. These coatings are characterized by X-Ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy along with interfacial contact resistance measurements. Further, the coated SS plates have been tested in real time polymer electrolyte membrane fuel cell operation for their use as bipolar plates and their performances have been compared with the fuel cell comprising conventional graphite plates. A cell comprising Titanium Nitride, Gold and Plasma Nitride coated metallic plates exhibit a power density of 430, 720 & 268 mW cm⁻² respectively, at an operating fuel cell potential of 0.6 V. Gold coated metallic plate shows comparable polymer electrolyte membrane fuel cell performance in relation to conventional graphite plate.     

Electrical and thermal transport properties of vanadium oxide thin films on metallic bipolar plates for fuel cell applications

We have focused on the in-depth comparative evaluation of the suitability of electrically-induced thermal transport characteristics of highly disordered vanadium oxide thin films deposited onto metallic bipolar plates as an expeditious self-heating source for the successful cold-start of fuel cells in a subfreezing environment. To achieve this, sol–gel derived vanadium oxide thin films on the non-polished surface of 316L austenitic and 446M ferritic substrates have been fabricated by a dip-coating process. The effects of electrical properties on thermal energy dissipation rate of the as-synthesized thin films deposited onto 316L and 446M stainless steel plates were firstly investigated and compared with each other. Subsequently, a series of physical, chemical, and structural analyses of the thin films have been performed using several analytical techniques such as the ASTM D3359, the ASTM D5946, XPS, and FE-SEM. The most important finding of this study was that the electrical resistivity of the thin films on 446M ferritic substrate was extremely low on a level of 4.8% of the 316L sample at −20 °C, and then the surface temperature rise of the thin film on 316L austenitic substrates was approximately 21.8 times greater than that of 446M ferritic substrates under simulated cold starting conditions (i.e., at a current density of 0.1 A·cm⁻² at −20 °C). Therefore, we concluded that vanadium oxide thin films on 316L austenitic stainless steel plates appears to be more applicable than those of 446M ferritic substrates for the cold-start enhancement of fuel cells from the practical point of view.     

An experimental feasibility study of vanadium oxide films on metallic bipolar plates for the cold start enhancement of fuel cell vehicles

An experimental study of vanadium oxide polycrystalline films deposited onto 316L stainless steel bipolar plates as an efficient Joule heating source for fuel cell vehicles was conducted by carefully modulating the negative temperature coefficients of the electrical resistance of the films at subzero temperatures. To fabricate the thin films, a well-mixed precursor solution of vanadium alkoxide and organic cosolvent was prepared by the hydrolytic sol-gel route and then coated on the pre-cleaned flat surface of 316L stainless steel plates with natural passive oxide layers by a dip-coating method. Subsequently, the variation of the nonlinear electrical resistance of the thin film was measured simultaneously over a wide temperature range of −20 to 80 °C, allowing direct detection of the surface temperature of the thin films. In addition, the adhesion, microstructures, compositions, and morphologies of the vanadium oxide thin films were investigated using the ASTM D3359 method, XRD, FE-SEM, and XPS analyses. A remarkable result from this study was that a temperature increase of 41.65 °C was induced by significant Joule heating of the vanadium sesquioxide films on metallic bipolar plates, i.e. approximately 1.8-folded more than the minimum requirement of Joule heating, at a current density of 0.1 A·cm⁻² at −20 °C. Thus, it was concluded that thermal dissipation from the resistive vanadium oxide films with a negative temperature coefficient can be effectively used as a self-heating source to melt frozen water at subzero ambient temperatures, particularly for fuel cell vehicles.     

Numerical-experimental investigation of using rubber blank holder on wrinkling of metallic bipolar plates formed by stamping process

Stamping is the regarded as the best among manufacturing method of metallic bipolar plates considering its less production time and higher mass production capability. The present research studied the manufacturing of metallic bipolar plates with a parallel serpentine flow field made of a 304 stainless steel plate of 0.1 mm thickness via stamping. The wrinkling is a defect created in stamping these plates. It prevents the correct assembly of the plates and, hence, reduces the efficiency of the assembly. Accordingly, this paper first investigates the effects of using rubber blank holders on wrinkling reduction around the bipolar plates. Then, the influence of the geometric parameters of the rubber blank holder, such as the thickness, width, hardness, and compression percentage, are studied by the response surface methodology. Finally, the most appropriate path for the assembly of the plates in terms of wrinkling is selected. According to the results, a rubber blank holder reduces the wrinkles around the bipolar plate. Among the studied parameters, the compression percentage and hardness of the blank holder contributed most to the reduction in the wrinkling around these plates for better assembly. Furthermore, wrinkling decreases with an increase in the compression percentage, hardness, width, and thickness of the rubber blank holder throughout the selected paths at 3 mm and 6 mm distances. Among the distances selected on the plate edges, a distance of 6 mm from the edges is the best path for assembling the plates.     

Effect of manufacturing conditions on the corrosion resistance behavior of metallic bipolar plates in proton exchange membrane fuel cells

Metallic bipolar plates are one of the promising alternatives to the graphite bipolar plates in proton exchange membrane fuel cell (PEMFC) systems. In this study, stainless steel (SS304, SS316L, and SS430), nickel (Ni 270), and titanium (Grade 2 Ti) plates with an initial thickness of 51 μm were experimented as bipolar plate substrate materials in corrosion resistance tests. In addition to unformed blanks, SS316L plates were formed with stamping and hydroforming processes to obtain bipolar plates under different process conditions (stamping force, hydroforming pressure, stamping speed, hydroforming pressure rate). These bipolar plates, then, were subjected to corrosion tests, and the results were presented and discussed in detail. Potentiodynamic polarizations were performed to observe corrosion resistance of metallic bipolar plates by simulating the anodic and cathodic environments in the PEMFC. In order to determine the statistical significance of the corrosion resistance differences between different manufacturing conditions, analysis of variance (ANOVA) technique was used on the corrosion current density (I_corr, μA cm⁻²) values obtained from experiments. ANOVA for the unformed substrate materials indicated that SS430 and Ni have less corrosion resistance than the other substrate materials tested. There was a significant difference between blank (unformed) and stamped SS316L plates only in the anodic environment. Although there was no noteworthy difference between unformed and hydroformed specimens for SS316L material, neither of these materials meet the Department of Energy‘s (DOE) target corrosion rate of ≤1 μA cm⁻² by 2015 without coating. Finally, stamping parameters (i.e. speed and force levels) and hydroforming parameters (i.e. the pressure and pressure rate) significantly affected the corrosion behavior of bipolar plates.     

Investigation of the effect of carbon post- vs pre-coated metallic bipolar plates for PEMFCs – start-up and shut-down

In this work, the influence of increased potentials during the start-up/shut-down process on metallic bipolar plates (316L) with the coating system Cr/a-C based on graphite-like carbon is investigated. In comparison to commonly applied post-coated bipolar plates, a new low-cost manufacturing process based on pre-coated metal sheets for bipolar plates was evaluated. By developing a vehicle near start-up/shut-down cycle, a relative humidity of 140% and anode residence time of 0.94 s show the greatest damage potential of the cycle variations. After 2000 start-up/shut-down cycles, pre-coated metallic bipolar plates show no increased voltage loss compared to conventional coatings. Nevertheless, the resistances increase for Cr/a-C post- and pre-coating at the H₂ outlet. This correlates with an increased surface roughness of the bipolar plate but otherwise only minor surface changes can be observed. The coating variation has no effect on the extent of catalyst coated membrane thinning or increased content of metal ions.     

The performance of miniature metallic PEM fuel cells

A prototype of metallic PEM fuel cell with thin stainless steel bipolar plates was tested for their potential applications in portable electronic products. The flow field pattern was grown from the stainless steel plates by the electroforming process. The main flow channel has the dimensions of 300 μm (width) × 300 μm (depth). The dimensions of the micro-features were 100 μm width × 50 μm depth and 50 μm width × 50 μm depth. The material of the electroformed flow field pattern is nickel. A prototype of a single cell with total thickness of 2.6 mm, overall reaction area of 4 cm² and bipolar plate area of 16 cm² was assembled for this study. In order to improve its corrosion resistance, the bipolar plates were coated with 5 μm thick of multi-layered corrosion resistant material.     

Fabrication by vacuum die casting and simulation of aluminum bipolar plates with micro-channels on both sides for proton exchange membrane (PEM) fuel cells

Among manufacturing methods for bipolar plates, vacuum die casting is an ideal process because arbitrarily complicated shapes and mass production is possible with a high production rate. We report on the fabrication of bipolar plates with micro-channel arrays on both sides by vacuum die casting for use in proton exchange membrane (PEM) fuel cells. The formability, mechanical properties, and microstructures of samples fabricated under various experimental conditions—molten metal temperature, injection velocity, and vacuum assistance—are investigated, and the experimental and simulation results are compared. The die cavity, which is equal to the bipolar plate area, is 200 mm long, 200 mm wide, and 0.8 mm thick. The active area of the channel is 110 mm × 150 mm, and the total plate thickness is 1.1 mm (the width and depth of the channel are 1 and 0.3 mm, respectively). The cast material used in this study is Silafont-36 alloy (Al–Si–Mg–Mn). Good quality samples with very few casting defects are obtained under the following conditions: molten metal temperature of 700 °C; injection velocities for slow and fast shots of 0.3 and 2.5 m s⁻¹, respectively; and vacuum pressure of 30 kPa.     

Integration of design of experiment and finite element method for the study of geometrical parameters in metallic bipolar plates for PEMFCs

Bipolar plates are among the most important components of polymer electrolyte membrane fuel cells that are responsible for a high percentage of their weights and costs. Metals are a suitable replacement for thick graphite plates that require high machining costs. The present study investigates the manufacturing process of metallic bipolar plates with a thickness of 0.1 mm using the stamping process. One of the problems with the formation of metallic bipolar plates is their rupture during plastic deformation. This study is aimed to investigate the effects of the geometrical parameters of bipolar plates, including channel width, rib width, channel depth, draft angle, and corner radius, on the formation of sheets. By designing some experiments, the effect of each parameter on the thinning percentage and filling depth of the bipolar plates were evaluated. The required data is obtained using the commercial finite element code. The results show that the channel depth, draft angle, and corner radius have the most effect on the plate thinning. In addition, the corner radius and the draft angle have the highest effect on the maximum channel depth. Finally, the thinning percentage and the filling depth for other geometric parameters can be predicted by a mathematical equation.     

Corrosion resistance characteristics of stamped and hydroformed proton exchange membrane fuel cell metallic bipolar plates

Metallic bipolar plates have several advantages over bipolar plates made from graphite and composites due to their high conductivity, low material and production costs. Moreover, thin bipolar plates are possible with metallic alloys, and hence low fuel cell stack volume and mass are. Among existing fabrication methods for metallic bipolar plates, stamping and hydroforming are seen as prominent approaches for mass production scales. In this study, the effects of important process parameters of these manufacturing processes on the corrosion resistance of metallic bipolar plates made of SS304 were investigated. Specifically, the effects of punch speed, pressure rate, stamping force and hydroforming pressure were studied as they were considered to inevitably affect the bipolar plate micro-channel dimensions, surface topography, and hence the corrosion resistance. Corrosion resistance under real fuel cell conditions was examined using both potentiodynamic and potentiostatic experiments. The majority of the results exhibited a reduction in the corrosion resistance for both stamped and hydroformed plates when compared with non-deformed blank plates of SS304. In addition, it was observed that there exist an optimal process window for punch speed in stamping and the pressure rate in hydroforming to achieve improved corrosion resistance at a faster production rate.     

Chemically stable electrospun NiCu nanorods@carbon nanofibers for highly efficient dehydrogenation of ammonia borane

We describe the preparation of bimetallic NiCu nanorods (NRs) incorporated on carbon nanofibers (NFs). The synthesis nanofibers were prepared by low cost and facile technique; electrospinning. Typically, sol–gel consisting of nickel acetate, copper acetate, and poly (vinyl alcohol) was electrospun. Sintering of the electrospun nanofiber mats in argon atmosphere led to partial elimination of the utilized polymer and abnormal decomposition of the metallic acetates to finally produce NiCu nanorods incorporated in carbon nanofibers. The as-obtained nanofibers were characterized by SEM, FE-SEM, XRD, TGA, XPS, TEM, and TEM-EDX standard techniques. The introduced bimetallic nanofibers revealed superior catalytic activity toward hydrogen release from ammonia borane. Also, they showed a good chemical stability due to covering the bimetallic nanorods by carbon shells. Interestingly, nanofibers were reused for 6 successive cycles with good catalytic activity. Moreover, the prepared nanofibers showed low activation energy about 28.9 kJ/mol. Finally, development of new catalytic materials in the field of energy is considered as a key objective of the modern research.     

A new alloy design concept for austenitic stainless steel with tungsten modification for bipolar plate application in PEMFC

The feasibility of a new alloy design concept utilizing the principle of ‘tungsten bronze effect’ is critically evaluated for the development of metallic bipolar plates for proton exchange membrane fuel cell (PEMFC). An austenitic stainless steel (ASS) is modified with W and La to improve the stability of the passive film in an acidic environment as well as to reduce the contact resistance by the tungsten bronze effect. The experimental ASS containing W and La was evaluated in a simulated PEMFC environment of H₃PO₄ and H₂SO₄ solutions at 80 °C, and the electrical property was evaluated by performing a contact resistance test. The test results show that the ASS modified with W and La has good passive film stability for corrosion resistance and low contact resistance. The X-ray photoelectron spectroscopy (XPS) analysis clearly suggests the possibility of the tungsten bronze effect from the change in valency state of W⁶⁺ to W⁵⁺ in the passive film formed on the modified ASS. The feasibility of a new alloy design concept utilizing the ‘tungsten bronze effect’ is well demonstrated; however, more study is highly required for the development of metallic bipolar plates of PEMFC.     

Studies of the deformation styles of the rubber-pad forming process used for manufacturing metallic bipolar plates

Rubber pad forming as a novel stamping technique has been widely used in the deep drawing, bulging, blanking, and flanging processes. It is a feasible method for manufacturing metallic bipolar plates, the surface of which has multi-array flow channels. For a single channel's fabrication, there are two different deformation styles: concave and convex. In this paper, the deformation characteristics of the two deformation styles are analyzed in detail with numerical simulation and experimental methods. The proper application conditions of the concave and convex deformation styles used to fabricate a certain metallic bipolar plate have been determined. If the ratio of the channel width to the rib width w/s>1, the concave style is more appropriate; otherwise, the convex style is preferred. Based on this theory, a bipolar plate sample (w/s<1) is successfully manufactured by the convex rubber-pad forming process.     

Preparation and properties of high performance nanocomposite bipolar plate for fuel cell

This study aims at developing lightweight and high performance composite bipolar plates for use in polymer electrolyte membrane fuel cells (PEMFCs). The thin polymer composite bipolar plates (the thickness <1.5 mm) containing of vinyl ester resin, graphite powder, organoclay have been fabricated by bulk molding compound (BMC) process. Organoclay was prepared by ionic exchange of montmorillonite (MMT) with three different molecular weight (M_w) of poly(oxypropylene)-backboned diamine intercalating agents. Results indicate that the basal spacing and content of MMT varied with M_w of POP-diamines are critical in determining the resultant mechanical properties for bipolar plates. Flexural strength of MMT composite plates was increased from 30.21 to 45.66 MPa by adding 2 phr of MMT. The flexural strength of the plate was also ca. 38% higher than the pristine graphite plate as the basal spacing of MMT was increased from 1.71 to 5.43 nm. Meanwhile, the unnotched impact strength of the composite plates was increased from 58.11 to 80.21 J m⁻¹. The unnotched impact strength of the plate was ca. 30% higher than that of the original graphite plates as the basal spacing of MMT was increased from 1.71 to 5.43 nm. The limiting oxygen index (LOI) and the UL-94 test revealed that the bipolar plate possesses excellent flame retardant with LOI >50 and UL-94-V0. The thermal decomposition temperature of each MMT composite plate is also higher than 250 °C. In addition, the bulk electrical conductivity of the bipolar plate with different MMT contents and basal spacing of MMT is higher than 100 S cm⁻¹. The corrosion current is less than 10⁻⁷ A cm⁻². Results confirm that the addition of MMT leads to a significant improvement on the performance of the composite bipolar plate.     

Studies on the fabrication of metallic bipolar plates—Using micro electrical discharge machining milling

Owed to the advantages of highly precise and flexible machining, micro electrical discharge machining milling (micro EDM milling) can machine higher aspect ratio micro flow channels than the micro flow channels made from etching or deposition techniques, which have aspect ratio of only 0.5-0.7.This study reports on the production of micro flow channels in metallic bipolar plates, using micro EDM milling. Through the use of micro EDM milling with tungsten carbide electrodes, this study succeed in machining channels with a depth and rib width of 500 μm, and height of 300 μm, 600 μm (aspect ratio of 0.6 and 1.2), respectively, in a reaction area 20 mm × 20 mm, on 50 mm × 50 mm × 1 mm SUS 316L stainless steel.In single cell tests, the cell performance in metallic bipolar plates with aspect ratio of 1.2 is higher than that of other tests, and this result shows that the aspect ratio can promote performance of micro fuel cells. Moreover, under the same condition regarding cell size, single cell performance in metallic bipolar plates of aspect ratio of 1.2 with micro EDM milling in this study is higher than the performance in metallic bipolar plates with electroforming or electrochemical machining techniques, and the metallic bipolar plate can promote power per unit volume.     

Experimental study on the dynamic performance of an air-cooled proton exchange membrane fuel cell stack with ultra-thin metal bipolar plate

In this paper, a compact 3 kW air-cooled fuel cell stack consists of 95 single cells with metallic bipolar plate is designed. Compared with graphite bipolar plates, metal stamping bipolar plates are lighter in weight, smaller in size and faster in heat conduction, therefore the transient behaviors of the voltage and temperature of each cell are analyzed. The results show that the heat distribution of the air-cooled fuel cell is very uniform, and the temperature difference between the inlet and outlet of cathode air of the fuel cell is lower than 15 °C. The individual cell voltage uniformity percentage variation value reaches 7% when the drop in the loading current is over 25 A. Moreover, the voltage uniformity variation value is higher than 4% when the loading current output exceeds 35A. Thus, a large drop in loading and a high loading current easily increase the voltage uniformity variation value. Long-term continuous operation has a negative influence on the performance of the stack, especially the last fuel cell near the anode outlet. Anode purging can effectively alleviate the uniformity percentage variation in the voltages. The designed air-cooled fuel cell exhibits good performance and strong environmental adaptability.     

Molybdenum carbide coated 316L stainless steel for bipolar plates of proton exchange membrane fuel cells

Superior corrosion resistance and high electrical conductivity are crucial to the metallic bipolar plates towards a wider application in proton exchange membrane fuel cells. In this work, molybdenum carbide coatings are deposited in different thicknesses onto the surface of 316 L stainless steel by magnetron sputtering, and their feasibility as bipolar plates is investigated. The microstructure characterization confirms a homogenous, compact and defectless surface for the coatings. The anti-corrosion performance improves with the increase of the coating thickness by careful analysis of the potentiodynamic and potentiostatic data. With the adoption of a thin chromium transition layer and coating of a ∼1052 nm thick molybdenum carbide, an excellent corrosion current density of 0.23 μA cm⁻² is achieved, being approximately 3 orders of magnitude lower than that of the bare stainless steel. The coated samples also show a low interfacial contact resistance down to 6.5 mΩ cm² in contrast to 60 mΩ cm² for the uncoated ones. Additionally, the hydrophobic property of the coatings’ surface is beneficial for the removal of liquid water during fuel cell operation. The results suggest that the molybdenum carbide coated stainless steel is a promising candidate for the bipolar plates.     

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.     

Development of micro direct methanol fuel cells for high power applications

A micro direct methanol fuel cell (μDMFC) with active area of 1.625 cm² has been developed for high power portable applications and its electrochemical characterization carried out in this study. The fragility of the silicon wafer makes it difficult to compress the cell for good sealing and hence to reduce contact resistance in the Si-based μDMFC. We have instead used very thin stainless steel plates as bipolar plates with the flow field machined by photochemical etching technology. For both anode and cathode flow fields, widths of both the channel and rib were 750 μm, with a channel depth of 500 μm. A gold layer was deposited on the stainless steel plate to prevent corrosion. This study used an advanced MEA developed in-house featuring a modified anode backing structure with a compact microporous layer. Maximum power density of the micro DMFC reached 62.5 mW cm⁻² at 40 °C, and 100 mW cm⁻² at 60 °C at atmospheric pressure, which almost doubled the performance of our previous Si-based μDMFC.     

Hydrogen absorption and optical properties of Pd/Mg thin films prepared by DC magnetron sputtering

Hydrogen storage in metallic thin films in the form of metal hydride have a great potential to solve the hydrogen storage challenges and also thin films offer an opportunity to grow new samples fast with novel structures. In the present work the ex situ study on structural, optical and hydrogen storage properties of Pd-capped Mg thin films have been investigated. The nano structured Pd-capped Mg thin films have been prepared by DC magnetron sputtering on glass substrate. The as deposited and hydrogenated samples have been characterized by XRD and FESEM. The content of hydrogen in thin films has measured by using Elastic Recoil Detection Analysis (ERDA) technique with 120 MeV₁₀₇ Ag⁺⁹ ions. The temperature dependent hydrogen contents in thin film samples have been estimated and the saturation of hydrogen absorption has been observed at 250 °C among all studied samples. In the optical reflectance spectra, Mg hydride samples have been observed partially transparent in comparison to as deposited Mg film.