Effect of chemical and heat treatment on the interfacial contact resistance and corrosion resistance of 446M ferritic stainless steel as a bipolar plate for polymer electrolyte membrane fuel cells

The bipolar plate is an important component of the polymer electrolyte membrane fuel cell (PEMFC) because it supplies the pathway of the electron flow between each unit cell. The ferritic stainless steel is considered a good candidate material for bipolar plate, but it is limited to use as a bipolar plate due to its corrosion problem and high interfacial contact resistance (ICR). To explore a cost-effective method of surface modification, various chemical and heat treatments are performed with 446M ferritic stainless steel to understand the effect of the surface modifications on the ICR and the corrosion resistance. The ICR and corrosion resistance of 446M stainless steel can be effectively controlled by a proper surface modification with combined treatment of immersion in the acidic solution, followed by heat treatment. The combined chemical and heat treatment not only improves the corrosion resistance but also reduces the ICR value.     

Effects of thermal oxi-nitridation on the corrosion resistance and electrical conductivity of 446M stainless steel for PEMFC bipolar plates

Stainless steel has attracted interest as a bipolar plate material for polymer electrolyte membrane fuel cells due to its excellent mechanical properties, good corrosion resistance, and low cost. However, the application of thermal nitridation for the improvement of electrical conductivity deteriorates the corrosion resistance under PEMFC operating conditions due to the discontinuous formation of external Cr-nitride. In this study, nitridation with pre-oxidation of 446M stainless steel was performed in order to improve both the corrosion resistance and the electrical conductivity. 446M stainless steels with oxide and nitride on the surface were evaluated to assess their feasibility as a bipolar plate material for PEMFCs. The results were compared with those obtained using as-received and only nitrided 446M stainless steels. The oxide formed by the pre-oxidation protects the surface of 446M stainless steel from corrosion in corrosive environments, especially under cathode conditions, and the Cr-nitride formed by the subsequent nitridation serves as an electro-conductive channel. As a result, the pre-oxidized, nitrided 446M stainless steel exhibits improved corrosion properties and electrical conductivity under PEMFC operating environments.     

Corrosion behavior of TiN-coated stainless steel as bipolar plate for proton exchange membrane fuel cell

Stainless steel is a potential material to be used as the bipolar plate for proton exchange membrane fuel cell (PEFC) because of its suitable physical and mechanical properties. Several coating techniques have been applied to improve its corrosion resistance. But seldom study is focused on the microstructure evolution with corrosion. In the present study, the use of TiN-coated stainless steel as the bipolar plate is evaluated. Two surface coating techniques, pulsed bias arc ion plating (PBAIP) and magnetron sputtering (MS), are adoped to prepare the TiN-coated stainless steel. Their corrosion resistances and electrical conductivities of the coated substrates are evaluated. The performance shows strong dependance on microstructural characteristics. The corrosion of SS304/Ti₂N/TiN prepared by MS mainly occurs on the grain boundary. The corrosion of SS304/TiN prepared by PBAIP mainly takes place from the large particles on the coating. The Ti₂N/TiN multilayer coating provides superb corrosion protective layer for stainless steel. Both the TiN and Ti₂N/TiN coatings provide low contact resistance.     

Optimized Cr-nitride film on 316L stainless steel as proton exchange membrane fuel cell bipolar plate

Pulsed bias arc ion plating was used to form Cr-nitride films on stainless steel as bipolar plate of proton exchange membrane fuel cell. Surface micrograph, film thickness, film composition, corrosion resistance, interfacial conductivity and contact angle with water of the sample obtained at the optimal flow rate of N₂ were investigated. The atomic ratio of Cr to N was close to 2:1 and the CrN phase with crystal planes of (111), (200), (220) and (311) was found in the film. Potentiodynamic and potentiostatic tests showed that the corrosion resistance of the bipolar plate sample was greatly enhanced. The contact resistance between the bipolar plate sample and Toray carbon paper was about two orders of magnitude lower than that of 316L stainless steel. The contact angle of the sample with water was 95°, which is beneficial for water management in fuel cells.     

Ag–polytetrafluoroethylene composite coating on stainless steel as bipolar plate of proton exchange membrane fuel cell

Forming a coating on metals by surface treatment is a good way to get high performance bipolar plate of proton exchange membrane fuel cell (PEMFC). In our research, Ag–polytetrafluoroethylene (PTFE) composite film was electrodeposited with silver-gilt solution of nicotinic acid by a bi-pulse electroplating power supply on 316 L stainless steel bipolar plate of PEMFC. Surface topography, contact angle, interfacial conductivity and corrosion resistance of the bipolar plate samples were investigated. Results showed that the defects on the Ag–PTFE composite coating are greatly reduced compared with those on the pure Ag coating fabricated under the same condition; and the contact angle of the Ag–PTFE composite coating with water is 114°, which is much bigger than that of the pure Ag coating (73°). In addition, the interfacial contact resistance of the composite coating stays as low as the pure Ag coating; and the bipolar plate sample with composite coating shows a close corrosion resistance to the pure Ag coating sample in potentiodynamic and potentiostatic tests. Coated 316 L stainless steel plate with Ag–PTFE composite coating exhibits well hydrophobic characteristic, less defects, high interfacial conductivity and good corrosion resistance, which shows a great potential of the application in PEMFC.     

The effect of pH and halides on the corrosion process of stainless steel bipolar plates for proton exchange membrane fuel cells

Stainless steel is attractive as material for bipolar plates in proton exchange membrane fuel cells, due to its high electrical conductivity, high mechanical strength and relatively low material and processing cost. Potentiostatic and potentiodynamic tests were performed in H₂SO₄ solutions on AISI 316L stainless steel bipolar plates with etched flow fields. The effect of pH and presence of small amounts of fluoride and chloride on the corrosion rate and interfacial contact resistance of the stainless steel bipolar plate were investigated. The tests performed in electrolytes with various pH values revealed that the oxide layer was thinner and more prone to corrosion at pH values significantly lower than the pH one expects the bipolar plate to experience in an operating proton exchange membrane fuel cells. The use of solutions with very low pH in such measurements is thus probably not the best way of accelerating the corrosion rate of stainless steel bipolar plates. By use of strongly acidic solutions the composition and thickness of the oxide layer on the stainless steel is probably altered in a way that might never have happened in an operating proton exchange membrane fuel cell. Additions of fluoride and chloride in the amounts expected in an operating fuel cell (2 ppm F⁻ and 10 ppm Cl⁻) did not cause significant changes for neither the polarization- nor the contact resistance measurements. However, by increasing the amount of Cl⁻ to 100 ppm, pitting was initiated on the stainless steel surface.     

Effect of manufacturing processes on contact resistance characteristics of metallic bipolar plates in PEM fuel cells

In this study, metallic bipolar plate (BPP) samples manufactured with stamping and hydroforming under different process conditions were tested for their electrical contact resistance characteristics to reveal the effect of manufacturing type and conditions. Punch speed and force in stamping, and pressure and pressure rate in hydroforming were selected as variable process parameters. In addition, two different channel sizes were tested to expose the effect of BPP micro-channel geometry and its consequences on the contact resistance. As a general conclusion, stamped BPPs showed higher contact conductivity than the hydroformed BPPs. Moreover, pressure in hydroforming and geometry had significant effects on the contact resistance behavior of BPPs. Short term corrosion exposure was found to decrease the contact resistance of bipolar plates. Results also indicated that contact resistance values of uncoated stainless steel BPPs are significantly higher than the respective target set by U.S. Department of Energy. Conforming to literature, proper coating or surface treatments are necessary to satisfy the requirements.     

Carbon-coated stainless steel as PEFC bipolar plate material

Stainless steel is quite attractive as bipolar plate material for polymer electrolyte fuel cells (PEFCs). Passive film on stainless steel protects the bulk of it from corrosion. However, passive film is composed of mixed metal oxides and causes a decrease in the interfacial contact resistance (ICR) between the bipolar plate and gas diffusion layer. Low ICR and high corrosion resistance are both required. In order to impart low ICR to stainless steel (SUS304), carbon-coating was prepared by using plasma-assisted chemical vapor deposition. Carbon-coated SUS304 was characterized by Raman spectroscopy and atomic force microscopy. Anodic polarization behavior under PEFC operating conditions (H₂SO₄ solution bubbled with H₂ (anode)/O₂ (cathode) containing 2 ppm HF at 80 °C) was examined. Based on the results of the ICR evaluated before and after anodic polarization, the potential for using carbon-coated SUS304 as bipolar plate material for PEFC was discussed.     

Effects of CrN/Cr coating layer on durability of metal bipolar plates under a fuel recirculation system of direct methanol fuel cells

Effects of a CrN/Cr coating layer on the durability of metal bipolar plates (stainless steel (STS) 430) are investigated in direct methanol fuel cells (DMFCs) with a fuel recirculation system, since under fuel recirculation the metal bipolar plates can be faced with a tougher corrosion environment. Before the fuel recirculation, the performance losses of the cells consisting of metal bipolar plates are ascribed to cathode degradation, due to a high corrosion level of the cathode side. However, after fuel recirculation, corrosion of the anode metal bipolar plate by pH decrease and overpotential increase brings about severe anode degradation. It is found that damage by corrosion of the cathode metal bipolar plate is limited to degradation of the cathode catalyst, whereas corrosion of the anode metal bipolar plate deteriorates not only the catalysts but also the electrolyte membrane. These durability tests show that the CrN/Cr coatings deposited on the STS 430 improve the corrosion resistance of the metal substrate and lead to low performance degradation.     

Active screen plasma nitriding of 316 stainless steel for the application of bipolar plates in proton exchange membrane fuel cells

Proton exchange membrane fuel cell (PEMFC) has attracted considerable interest because of its superb performance, and many researches are focused on the development of high-performance, long-life bipolar plates. Stainless steel bipolar plates offer many advantages over the conventional graphite bipolar plates, such as low material and fabrication cost, excellent mechanical behaviour and ease of mass production. However, the insufficient corrosion resistance and relatively high interfacial contact resistance (ICR) become the major obstacles to the widespread use of stainless steel bipolar plates. In this work, active screen plasma nitriding (ASPN), a novel plasma nitriding technique, was used to modify the surface of 316 austenitic stainless steel. A variety of analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), glow discharge optical emission spectrometer (GDOES), were employed to characterize the nitrided samples. The results reveal that a nitrogen supersaturated S-phase layer has been successfully produced on the surface of all nitrided 316 stainless steel samples. The interfacial contact resistance (ICR) value can be decreased dramatically after ASPN treatment and the corrosion resistance can also been improved. In addition, better corrosion resistance can be achieved by active screen plasma nitriding with a stainless steel screen than with a carbon steel screen. This technique could be used to improve the performance and lifespan of bipolar plates for fuel cells.     

Thermal nitridation of chromium electroplated AISI316L stainless steel for polymer electrolyte membrane fuel cell bipolar plate

The electrical and corrosion properties of surface-nitrided AISI316L stainless steel are evaluated to assess the potential use of this material as a bipolar plate for a polymer electrolyte membrane fuel cell. Chromium is electroplated on the surface of the AISI316L stainless steel before nitridation. The nitriding condition is selected so as to form Cr₂N nitride only and the result is compared with that of a CrN + Cr₂N nitride coating. The stainless steels with the Cr₂N nitride protective coating layer exhibit better interfacial contact resistance and corrosion resistance than the as-rolled or (CrN + Cr₂N)-coated AISI316L stainless steels.     

Evaluation of Ni-Cr-P coatings electrodeposited on low carbon steel bipolar plates for polymer electrolyte membrane fuel cell

Polymer electrolyte membrane fuel cell (PEMFC) stacks suffer from the high cost and low volumetric energy of non-porous graphite bipolar plates. To resolve this problem, a bilayer coating consisting of Ni and Ni–Cr–P is deposited on AISI 1020 low-carbon steel using pulse electrodeposition. Ni/Ni–Cr–P-coated AISI 1020 is evaluated as a bipolar plate material for PEMFCs. Ni/Ni–Cr–P-coated substrates exhibit better corrosion resistance in both cathodic (air-purging) and anodic (H₂-purging) environment than the bare AISI 1020 substrate and lower interfacial contact resistance (ICR) than bare AISI 1020 and stainless steel. Further, it is expected to show better water management as the Ni/Ni–Cr–P coating is more hydrophobic than the bare substrate. Preliminary studies show that Ni/Ni–Cr–P-coated AISI 1020 plate can be a suitable candidate for replacing graphite as the bipolar plate of PEMFCs.     

Effect of substrate material on the corrosion of TiN-coated stainless steels in simulated anode and cathode environments of proton exchange membrane fuel cells

A physical vapor deposition (PVD) TiN coating has been used to increase the corrosion resistance of two stainless steel materials for bipolar plate application in proton exchange membrane fuel cells (PEMFCs). Our earlier studies had shown that a TiN coating on SS410 and SS316L increased the corrosion resistance of SS410 and SS316L significantly. In this study, we examine how the substrate affects the corrosion of TiN-coated stainless steel in the simulated anode and cathode environments. Potentiodynamic and contact resistance test results show that the polarization resistance and contact resistance of TiN-coated SS410 and TiN-coated SS316L are almost the same. However, in the simulated anode condition, the corrosion current density of TiN-coated SS410 is positive and the corrosion current density of TiN-coated SS316L is negative. Inductively coupled plasma optical emission spectrometry (ICP-OES) test results also show that the metal ion concentration is much higher for TiN-coated SS410 at the anode side. At the cathode side, the potentiostatic and ICP-OES tests show that the corrosion of TiN-coated SS410 and TiN-coated SS316L are in the same range. Therefore, the substrate has an effect on corrosion in the simulated anode working conditions of PEMFCs. In order to be the suitable bipolar plate materials, both the coating and substrate need to have a higher corrosion resistance.     

Pre-oxidized and nitrided stainless steel alloy foil for proton exchange membrane fuel cell bipolar plates: Part 1. Corrosion, interfacial contact resistance, and surface structure

Thermal (gas) nitridation of stainless steel alloys can yield low interfacial contact resistance (ICR), electrically conductive and corrosion-resistant nitride containing surface layers (Cr₂N, CrN, TiN, V₂N, VN, etc.) of interest for fuel cells, batteries, and sensors. This paper presents results of scale-up studies to determine the feasibility of extending the nitridation approach to thin 0.1 mm stainless steel alloy foils for proton exchange membrane fuel cell (PEMFC) bipolar plates. Developmental Fe-20Cr-4V alloy and type 2205 stainless steel foils were treated by pre-oxidation and nitridation to form low-ICR, corrosion-resistant surfaces. As-treated Fe-20Cr-4V foil exhibited target (low) ICR values, whereas 2205 foil suffered from run-to-run variation in ICR values, ranging up to 2× the target value. Pre-oxidized and nitrided surface structure examination revealed surface-through-layer-thickness V-nitride particles for the treated Fe-20Cr-4V, but near continuous chromia for treated 2205 stainless steel, which was linked to the variation in ICR values. Promising corrosion resistance was observed under simulated aggressive PEMFC anode- and cathode-side bipolar plate conditions for both materials, although ICR values were observed to increase. The implications of these findings for stamped bipolar plate foils are discussed.     

Conducting polymer-coated stainless steel bipolar plates for proton exchange membrane fuel cells (PEMFC)

Stainless steel satisfies many of the requirements for proton exchange membrane (PEM) fuel cell bipolar plates except its corrosion under fuel cell operating conditions. Metal oxide formation leads to contact resistance, and metal dissolution can cause contamination of the membrane electrode assembly (MEA). These problems can be solved by coating stainless steel plates with corrosion resistant and conductive layers. In this study, 304 stainless steel was coated electrochemically with the conducting polymers polyaniline (PANI) and polypyrrole (PPY). Cyclic voltammetry was used for the polymerization and deposition of these polymers. The polymer-coated stainless steel plates were tested for corrosion and contact resistance under PEM fuel cell conditions, which showed improved corrosion resistance with acceptable contact resistance.     

Formable chromium nitride coatings for proton exchange membrane fuel cell stainless steel bipolar plates

Among the different coatings developed for proton exchange membrane fuel cell steel bipolar plate, nitride-based coatings present several advantages compared to gold or polymeric coating: high chemical stability, low interfacial contact resistance and reasonable cost. In this work, 50 nm thick chromium nitride coatings are deposited by reactive magnetron sputtering on 316L stainless steel foil. They are optimized to fulfill the Department of Energy targets in terms of interfacial contact resistance (ICR) and corrosion resistance, with values of 8.4 mΩ cm⁻² (at 100 N cm⁻²) and 0.10 μA cm⁻² (in 0.6 M H₂SO₄ solution at 0.48 V_vs. SCE potential) respectively. Moreover, they retain their excellent properties after high deformation (biaxial deformation of 20% in x-axis and 5% in y-axis), giving the possibility to achieve, in line, the stamping of a bipolar plate from a coated foil. The etching of the substrate, prior to the coating deposition, appears to be determinant to obtain low and stable corrosion current and ICR. The removing of interfacial oxyde leads to better coating adhesion and improves the corrosion resistance and electrical conductivity. The enhancement of the properties (low ICR and high corrosion resistance) is durable, with no signicant change of the ICR value up to 200 days after deposition.     

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.     

Applicability of extra low interstitials ferritic stainless steels for bipolar plates of proton exchange membrane fuel cells

Ferritic stainless steels can be attractive bipolar plate materials of proton exchange membrane fuel cells (PEMFC), provided that the stainless steels show sufficient corrosion resistance, for instance, by eliminating interstitial elements such as carbon and nitrogen. In the present study, thus, ferritic stainless steels (19Cr2Mo and 22Cr2Mo) with extra low interstitials (ELI) are evaluated to determine the required level of chromium content to apply them for PEMFC bipolar plates. In a simulated PEMFC environment (0.05 M SO₄²⁻ (pH 3.3) + 2 ppm F⁻ solution at 353 K), the 22Cr2Mo stainless steel showed lower current density during the polarization in comparison with the 19Cr2Mo one. The polarization behavior of the 22Cr2Mo stainless steel resembles that of the type 316 one (17Cr12Ni2Mo). Similar values of interfacial contact resistance (ICR) are observed for both ferritic stainless steels. The 22Cr2Mo stainless steel bipolar plate is found to be stable throughout the cell operation, while the 19Cr2Mo stainless steel corroded within 1000 h. After the cell operation, the 22Cr2Mo stainless steel retains the chromium enriched passive film, while the chromium enriched surface film is not found for the 19Cr2Mo one, showing iron oxide/hydroxide based film. X-ray fluorescence (XRF) analysis of the membrane electrode assemblies (MEAs) after the cell operation indicates that the 22Cr2Mo stainless steel was less contaminated with iron species. The above results suggest that the 22Cr2Mo stainless steel can be applicable to bipolar plates for PEMFC, especially 22 mass% of chromium content in ferritic stainless steel with ELI system is, at least, demanded to ensure stable cell performance.     

Preparation of Cr-based multilayer coating on stainless steel as bipolar plate for PEMFCs by magnetron sputtering

In the present study, a multilayer composing of Cr₃Ni₂/Cr₂N/CrN is sputtered onto stainless steel. The potential of using the coated stainless steel as the bipolar plate for polymer electrolyte membrane fuel cell (PEMFC) is evaluated. The coated stainless steel exhibits improved corrosion resistance and higher electrical conductivity. The coated surface also demonstrates a hydrophobic characteristic. By using single cell test, the multilayer-coated SS304 plate exhibits an improved performance in terms of I-V properties.     

Corrosion study of SS430/Nb as bipolar plate materials for PEMFCs

Niobium-coated 430 stainless steel (SS430/Nb) specimens were evaluated as possible bipolar plate materials in conditions that resemble a typical PEMFC environment with respect to their interfacial contact resistance (ICR) and corrosion resistance. Results show that SS430/Nb demonstrated to have low ICR values and very good corrosion resistance in comparison with commercial steel and Ni-based alloys. In addition, the ICR values are also comparable with those of graphite.