Corrosion resistance and interfacial contact resistance of TiN coated 316L bipolar plates for proton exchange membrane fuel cell

TiN coating is successfully deposited on 316L by multi-arc ion plating. Corrosion behavior of TiN coated 316L is studied in 0.05 M H₂SO₄ + 2 ppm F⁻ simulating proton exchange membrane fuel cell (PEMFC) environments using electrochemical method, and interfacial contact resistance (ICR) is measured before and after potentiostatic polarization at operation potential for PEMFC. The TiN coated 316L exhibits promising ICR and improved corrosion resistance in simulated aggressive PEMFC environments. Only general overall corrosion is observed after potentiostatic polarization. Stable passive film has formed on the surface of the TiN coated 316L after potentiostatic polarization at the operation potential and results in a slight increase in the ICR. These results indicate that the TiN coated 316L is a candidate bipolar plate material for PEMFC stacks.     

Anticorrosion properties of Ta-coated 316L stainless steel as bipolar plate material in proton exchange membrane fuel cells

In order to reduce the cost, volume and weight of the bipolar plates used in the proton exchange membrane fuel cells (PEMFC), more attention is being paid to metallic materials, among which 316L stainless steel (SS316L) is quite attractive. In this study, metallic Ta is deposited on SS316L using physical vapor deposition (PVD) to enhance the corrosion resistance of the bipolar plates. Simulative working environment of PEMFC is applied for testing the corrosion property of uncoated and Ta-coated SS316L. X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods (potentiodynamic and potentiostatic polarization) are also used for analyzing characteristics of uncoated and Ta-coated SS316L. Results show that, Ta-coated SS316L has significantly better anticorrosion property than that of uncoated SS316L, with corrosion current densities of uncoated SS316L being 44.61 μA cm⁻² versus 9.25 μA cm⁻² for Ta-coated SS316L, a decrease of about 5 times. Moreover, corrosion current densities of Ta-coated SS316L in both simulative anode (purged with H₂) and cathode (purged with air) conditions are smaller than those of uncoated SS316L.     

Chromium nitride/Cr coated 316L stainless steel as bipolar plate for proton exchange membrane fuel cell

Chromium nitride/Cr coating has been deposited on surface of 316L stainless steel to improve conductivity and corrosion resistance by physical vapor deposition (PVD) technology. Electrochemical behaviors of the chromium nitride/Cr coated 316L stainless steel are investigated in 0.05 M H₂SO₄ + 2 ppm F⁻ simulating proton exchange membrane fuel cell (PEMFC) environments, and interfacial contact resistance (ICR) are measured before and after potentiostatic polarization at anodic and cathodic operation potentials for PEMFC. The chromium nitride/Cr coated 316L stainless steel exhibits improved corrosion resistance and better stability of passive film either in the simulated anodic or cathodic environment. In comparison to 316L stainless steel with air-formed oxide film, the ICR between the chromium nitride/Cr coated 316L stainless steel and carbon paper is about 30 mΩ cm² that is about one-third of bare 316L stainless steel at the compaction force of 150 N cm⁻². Even stable passive films are formed in the simulated PEMFC environments after potentiostatic polarization, the ICR of the chromium nitride/Cr coated 316L stainless steel increases slightly in the range of measured compaction force. The excellent performance of the chromium nitride/Cr coated 316L stainless steel is attributed to inherent characters. The chromium nitride/Cr coated 316L stainless steel is a promising material using as bipolar plate for PEMFC.     

High-density plasma nitriding of AISI 316L for bipolar plate in proton exchange membrane fuel cell

Austenitic stainless steel (AISI 316L) is nitrided by inductively coupled plasma using a gas mixture of N₂ and H₂ at temperatures between 530 K and 650 K, and the corrosion resistance as well as the interfacial contact resistance (ICR) are measured in a simulated proton exchange membrane fuel cell (PEMFC) environment.After plasma nitriding, a nitrogen-expanded austenite layer, the so-called S-phase is formed in all nitrided samples. The ICR value of the nitrided samples decreases to approximately 10 mΩcm² after plasma nitriding. The sample nitrided at 590 K shows the best corrosion property, while the corrosion resistance of the sample nitrided at higher temperatures decreases because of the formation of Cr-depleted regions in the nitrided sample. By using high-density plasma, the process temperature can be reduced to such a low temperature that Cr depletion is not significant, but a dense S-phase is formed.     

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.     

Tantalum nitride coated AISI 316L as bipolar plate for polymer electrolyte membrane fuel cell

Tantalum nitride (TaN) thin films are deposited on AISI 316L stainless steel by inductively coupled, plasma-assisted, reactive magnetron sputtering at various N₂ flow rates. TaN film behavior is investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) conditions by using electrochemical measurement techniques for application as bipolar plates. The results of a potentio-dynamic polarization test under PEMFC cathodic and anodic conditions indicate that the corrosion current density of the TaN_x films is of the order of 10⁻⁷ A cm⁻² (at 0.6 V) and 10⁻⁸ A cm⁻² (at −0.1 V), respectively; these results are considerably better than the individual results for metallic Ta films and AISI 316L stainless steel. The TaN_x films exhibit superior stability in a potentio-static polarization test performed under PEMFC cathodic and anodic conditions. The interfacial contact resistance of the films is measured in the range of 50-150 N cm⁻², and the lowest value is 11 mΩ cm² at a compaction pressure of 150 N cm⁻².     

Carbon-based films coated 316L stainless steel as bipolar plate for proton exchange membrane fuel cells

Carbon-based films on 316L stainless steel were prepared as bipolar plates for proton exchange membrane fuel cells (PEMFCs) by pulsed bias arc ion plating. Three kinds of films were formed including the pure C film, the C–Cr composite film and the C–Cr–N composite film. Interfacial conductivity of the bipolar plate with C–Cr film was the highest, which showed great potential of application. Corrosion tests in simulated PEMFC environments revealed that the C–Cr film coated sample always showed better anticorrosive performance than 316L stainless steel either in reducing or oxidizing environments. The C–Cr film coated bipolar plate sample also had high surface energy. The contact angle of the C–Cr film coated sample with water was 92°, which is beneficial for water management in a fuel cell.     

Improvement of corrosion and electrical conductivity of 316L stainless steel as bipolar plate by TiN nanoparticle implantation using plasma focus

The present work reports the results of TiN-ions implantation into the SS316L samples as bipolar plates by a 4 kJ Mather type Plasma Focus (PF) device operated with nitrogen gas for 10, 20, and 30 shots in order to improve the corrosion resistance and electrical conductivity of samples. The PF can generate short lived (10–100 ns) but high temperature (0.1–2.0 keV) and high density (10¹⁸–10²⁰ cm⁻³) plasma, and the whole process of PF lasts just a few microseconds. X-ray diffraction (XRD) results reveal the formation of a nanocrystalline titanium nitride coating on the surface of substrate. The interfacial contact resistance (ICR) of samples is measured, and the results show that the conductivity of samples increase after coating because of high electrical conductivity of TiN coating. The electrochemical results show that the corrosion resistances are significantly improved when TiN films are deposited into SS316L substrate. The corrosion potential of the TiN coated samples increases compared with that of the bare SSI316L and corrosion currents decrease in TiN implanted samples. Scanning Electron Microscopy (SEM) indicates changes in surface morphology before and after potentiostatic test. The thickness of coated layer which is obtained by cross sectional SEM is about 19 μm.     

An investigation into nickel implanted 316L stainless steel as a bipolar plate for PEM fuel cell

A nickel-rich layer about 100 μm in thickness with improved conductivity was formed on the surface of austenitic stainless steel 316L (SS316L) by ion implantation. The effect of ion implantation on the corrosion behavior of SS316L was investigated in 0.5 M H₂SO₄ with 2 ppm HF solution at 80 °C by potentiodynamic test. In order to investigate the chemical stability of the ion implanted SS316L, the potentiostatic test was conducted in an accelerated cathode environment and the solutions after the potentiostatic test were analyzed by inductively coupled plasma atomic emission spectrometer (ICP-AES). The results of potentiodynamic test show that the corrosion potential of SS316L is shifted toward the positive direction from −0.3 V versus SCE to −0.05 V versus SCE in anode environment and the passivation current density at 0.6 V is reduced from 11.26 to 7.00 μA cm⁻² in the cathode environment with an ion implantation dose of 3 × 10¹⁷ ions cm⁻². The potentiostatic test results indicate that the nickel implanted SS316L has higher chemical stability in the accelerated cathode environment than the bare SS316L, due to the increased amount of metallic Ni in the passive layer. The ICP results are in agreement with the electrochemical test results that the bare SS316L has the highest dissolution rate in both cathode and anode environments and the Ni implantation markedly reduces the dissolution rate. A significant improvement of interfacial contact resistance (ICR) is achieved for the SS316L implanted with nickel as compared to the bare SS316L, which is attributed to the reduction in passive layer thickness caused by the nickel implantation. The ICR values for implanted specimens increase with increasing dose.     

Improved corrosion resistance and interfacial contact resistance of 316L stainless-steel for proton exchange membrane fuel cell bipolar plates by chromizing surface treatment

The electrochemical performance and electrical contact resistance of chromized 316 stainless-steel (SS) are investigated under simulated operating condition in a proton-exchange membrane fuel cell (PEMFC). The corrosion resistance of the chromized stainless steel is assessed by potentiodynamic and potentiostatic tests and the interfacial contact resistance (ICR) is examined by measuring the electrical contact resistance as a function of the compaction force. The results show that the chromizing surface treatment improves the corrosion resistance of the stainless steel due to the high-chromium concentration in the diffuse coating layer. On the other hand, the excess Chromium content on the surface increases the contact resistance of the steel plate to a level that is excessively high for commercial applications. This study examines the root cause of the high-contact resistance after chromizing and reports the optimum process to improve the corrosion resistance without sacrificing the ICR by obtaining a chrome carbide on the outer layer.     

Effect of fluoride ions on corrosion behavior of SS316L in simulated proton exchange membrane fuel cell (PEMFC) cathode environments

In order to determine the suitability of SS316L as a bipolar plate material in proton exchange membrane fuel cells (PEMFCs), its corrosion behavior is studied under different simulated PEMFC cathode corrosion conditions. Solutions of 1 × 10⁻⁵ M H₂SO₄ with a wide range of different F⁻ concentrations at 70 °C bubbled with air are used to simulate the PEMFC cathode environment. Electrochemical methods, both potentiodynamic and potentiostatic, are employed to study the corrosion behavior. Scanning electron microscopy (SEM) is used to examine the surface morphology of the specimen after it is potentiostatic polarized under simulated PEMFC cathode environments. Auger electron spectroscopy (AES) analysis is used to identify the composition and the depth profile of the passive film formed on the SS316L surface after it is polarized in simulated PEMFC cathode environments. Photo-electrochemical (PEC) method and capacitance measurements are used to characterize the semiconductor passive films. The results of both the potentiodynamic and potentiostatic analyses show that corrosion currents increase with F⁻ concentrations. SEM examination results indicate that pitting occurs under all the conditions studied and pitting is more severe with higher F⁻ concentrations. From the results of AES analysis, PEC analysis and the capacitance measurements, it is determined that the passive film formed on SS316L is a bi-layer semiconductor, similar to a p-n heterojunction consisting of an external n-type iron oxide rich semiconductor layer (electrolyte side) and an internal p-type iron-chromium oxide semiconductor layer (metal side). Further analyses of the experimental results reveal the electronic structure of the passive film and shed light on the corrosion mechanisms of SS316L in the PEMFC cathode environment.     

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.     

Molybdenum nitride modified AISI 304 stainless steel bipolar plate for proton exchange membrane fuel cell

A molybdenum nitride diffusion coating has been prepared on the surface of AISI 304 stainless steel (304 SS) by plasma surface diffusion alloying method as bipolar plate for proton exchange membrane fuel cell (PEMFC). X-ray diffraction data shows that the molybdenum nitride is face-centered-cubic Mo₂N phase. The results of scanning electron microscopy in combination with energy-dispersive X-ray analysis spectrometer indicate that the as-prepared molybdenum nitride diffusion coating consists of a ∼3.5 μm surface layer (molybdenum nitride) and a ∼0.5 μm subsurface layer (Mo and N solid solution). In addition, the average contact angle with water for modified 304 SS is 91°, demonstrating the better hydrophobic property of the surface modified 304 SS as compared to the untreated ones with average contact angle of 68°. Potentiodynamic and potentiostatic testing in simulated PEFMC operating conditions (0.05 M H₂SO₄ + 2 ppm F⁻ solution at 70 °C purged with either hydrogen or air) as well as interfacial contact resistance (ICR) measurement imply that the molybdenum nitride modified 304 SS exhibits improved corrosion resistance and promising ICR.     

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.     

Effect of plasma nitriding on behavior of austenitic stainless steel 304L bipolar plate in proton exchange membrane fuel cell

A dense and supersaturated nitrogen layer with higher conductivity is obtained on the surface of austenitic stainless steel 304L by the low temperature plasma nitriding. The effect of plasma nitriding on the corrosion behavior and interfacial contact resistance (ICR) for the austenitic stainless steel 304L was investigated in 0.05 M H₂SO₄ + 2 ppm F⁻ simulating proton exchange membrane fuel cell (PEMFC) environment using electrochemical and electric resistance measurements. The experiment results show that the stable passive film is formed after the potentiostatic polarization at the specified anodic or cathodic potentials under PEMFC operation condition, and the plasma nitriding improves slightly the corrosion resistance and decreases markedly the ICR of 304L. The ICR of the plasma nitrided 304L increases after the potentiostatic polarizations for 4 h, and lower than 100 mΩ cm² at the compaction force of 150 N cm⁻².     

Improved anticorrosion properties and electrical conductivity of 316L stainless steel as bipolar plate for proton exchange membrane fuel cell by lower temperature chromizing treatment

The lower temperature chromizing treatment is developed to modify 316L stainless steel (SS 316L) for the application of bipolar plate in proton exchange membrane fuel cell (PEMFC). The treatment is performed to produce a coating, containing mainly Cr-carbide and Cr-nitride, on the substrate to improve the anticorrosion properties and electrical conductivity between the bipolar plate and carbon paper. Shot peening is used as the pretreatment to produce an activated surface on stainless steel to reduce chromizing temperature. Anticorrosion properties and interfacial contact resistance (ICR) are investigated in this study. Results show that the chromized SS 316L exhibits better corrosion resistance and lower ICR value than those of bare SS 316L. The chromized SS 316L shows the passive current density about 3E−7 A cm⁻² that is about four orders of magnitude lower than that of bare SS 316L. ICR value of the chromized SS 316L is 13 mΩ cm² that is about one-third of bare SS 316L at 200 N cm⁻² compaction forces. Therefore, this study clearly states the performance advantages of using chromized SS 316L by lower temperature chromizing treatment as bipolar plate for PEMFC.     

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.     

Aluminate cement/graphite conductive composite bipolar plate for proton exchange membrane fuel cells

Aluminate cement/graphite conductive composite bipolar plate for proton exchange membrane fuel cells (PEMFC) was prepared by mold pressing at room temperature. The effect of size of graphite particles on the conductivity and the flexural strength of composite bipolar plate were discussed. Resistance to acid corrosion, thermal property and pore size distribution of this composite bipolar plate were also investigated in this paper. The experiment results show that the conductivity and the flexural strength of this composite bipolar plate can be improved by choosing uniform size graphite as conductive fillers. The corrosion current is about 10^−4.5 A cm⁻² from polarization curves of this composite bipolar plate, which shows that this composite bipolar plate is acid corrosion-resistant. Al and Ca ions may leach from this composite bipolar plate after 1 M H₂SO₄ acid corrosion. But Al and Ca ions leaching from this composite bipolar plate are only a little percentage of the total Al and Ca ions content in the composite bipolar plate after acid corrosion at 30 °C. This composite bipolar plate is also thermally stable from room temperature to 400 °C. The large amount of pore in this composite bipolar plate is gel capillary pores because of the hydration and solidification of aluminate cement, which make it possess humidifying function during the PEMFC operating.     

Influence of heat treatment on corrosion behaviors of 316L stainless steel in simulated cathodic environment of proton exchange membrane fuel cell (PEMFC)

The influences of two types of heat-treatments on the corrosion behavior of 316L SS in the simulated cathodic environment of PEMFC, are investigated using potentiodynamic curve, electrochemical impedance spectroscopy (EIS), Mott-Schottky plot and auger electron spectroscopy (AES), respectively. The results show that 316L SS is in the passive state within the potential region from −0.1V_SCE to 0.8V_SCE in the simulated cathodic environment of PEMFC, and a passive film can be formed on 316L SS. The passivity of 316L SS in the simulated cathodic environment of PEMFC firstly increases and then degrades with the increased solid solution temperature or time, and the best passivity corresponds to the solid solution temperature at 1050 °C for 40 min among other solid solution treatments. While 316L SS heat-treated with the solid solution treatment at 1050 °C for 40 min plus aging treatment at 900 °C for 4 h, also has the best passivity in the same solution among other solid solution plus aging treatments. The best corrosion protection, lowest donor density and the highest thickness of the passive film corresponding to the solid solution temperature at 1050 °C for 40 min among other solid solution or solid solution plus aging heat treatments, and this treatment is mostly suitable for improving the anti-corrosion property of 316L SS in the simulated cathodic environment of proton exchange membrane fuel cell (PEMFC).     

The effect of temperature on corrosion behavior of SS316L in the cathode environment of proton exchange membrane fuel cells

The effect of temperature on the corrosion behavior of SS316L in simulated proton exchange membrane fuel cell (PEMFC) environments has been systematically studied. Electrochemical methods, both potentiodynamic and potentiostatic, are employed to characterize the corrosion behavior. Atomic force microscope (AFM) is used to examine the surface morphology and X-ray photoelectron spectroscopy (XPS) analysis is used to identify the composition and the depth profile of the passive film. Photo-electrochemical (PEC) measurements are also performed to determinate the band gap energy of the passive film semiconductor. Interfacial contact resistances (ICR) between polarized SS316L and carbon paper are also measured. The experimental results show that corrosion resistance decreases with temperatures even though the thickness of passive film increases with temperature, at a given cell potential, the corrosion behavior of SS316L can be significantly different at different temperatures in PEMFC cathode environments, and the band gap of passive films decrease with temperature. The results also show that within the temperature range studied (25-90 °C), after different passivation time, the corrosion current densities of SS316L are all lower than the US DOE 2015 target value of 1 μA cm⁻², but the ICR between the carbon paper and polarized SS316L does not satisfy the US DOE 2015 target.