An investigation into TiN-coated 316L stainless steel as a bipolar plate material for PEM fuel cells

In order to reduce the cost, weight and volume of the bipolar plates, considerable attention is being paid to developing metallic bipolar plates to replace the non-porous graphite bipolar plates that are in current use. However, metals are prone to corrosion in the proton exchange membrane (PEM) fuel cell environments, which decreases the ionic conductivity of the membrane and lowers the overall performance of the fuel cells. In this study, TiN was coated on SS316L using a physical vapor deposition (PVD) technology (plasma enhanced reactive evaporation) to increase the corrosion resistance of the base SS316L. X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods were used to characterize the TiN-coated SS316L. XRD showed that the TiN coating had a face-centered-cubic (fcc) structure. Potentiodynamic tests and electrochemical impedance tests showed that the corrosion resistance of SS316L was significantly increased in 0.5 M H₂SO₄ at 70 °C by coating with TiN. In order to investigate the suitability of these coated materials as cathodes and anodes in a PEMFC, potentiostatic tests were conducted under both simulated cathode and anode conditions. The simulated anode environment was −0.1 V versus SCE purged with H₂ and the simulated cathode environment was 0.6 V versus SCE purged with O₂. In the simulated anode conditions, the corrosion current of TiN-coated SS316L is −4 × 10⁻⁵ A cm⁻², which is lower than that of the uncoated SS316L (about −1 × 10⁻⁶ A cm⁻²). In the simulated cathode conditions, the corrosion current of TiN-coated SS316L is increased to 2.5 × 10⁻⁵ A cm⁻², which is higher than that of the uncoated SS316L (about 5 × 10⁻⁶ A cm⁻²). This is because pitting corrosion had taken place on the TiN-coated specimen.     

Conductive amorphous carbon-coated 316L stainless steel as bipolar plates in polymer electrolyte membrane fuel cells

Amorphous carbon (a-C) film about 3 μm in thickness is coated on 316L stainless steel by close field unbalanced magnetron sputter ion plating (CFUBMSIP). The AFM and Raman results reveal that the a-C coating is dense and compact with a small size of graphitic crystallite and large number of disordered band. Interfacial contact resistance (ICR) results show that the surface conductivity of the bare SS316L is significantly increased by the a-C coating, with values of 8.3–5.2 mΩ cm² under 120–210 N/cm². The corrosion potential (E_corr) shifts from about −0.3 V vs SCE to about 0.2 V vs SCE in both the simulated anode and cathode environments. The passivation current density is reduced from 11.26 to 3.56 μA/cm² with the aid of the a-C coating in the simulated cathode environment. The a-C coated SS316L is cathodically protected in the simulated anode environment thereby exhibiting a stable and lower current density compared to the uncoated one in the simulated anode environment as demonstrated by the potentiostatic results.     

Corrosion properties and contact resistance of TiN, TiAlN and CrN coatings in simulated proton exchange membrane fuel cell environments

In this study, the contact resistance (CR) and electrochemical properties of TiN, CrN and TiAlN electron beam physical vapor deposition (EBPVD) coatings and their stainless steel 316L (SS316L) substrate were investigated in a simulated proton exchange membrane (PEM) fuel cell environment. The potentiodynamic polarization corrosion tests were conducted at 70 °C in 1 M H₂SO₄ purged with either O₂ or H₂, and the potentiostatic corrosion tests were performed under both simulated cathodic (+0.6 V vs. Ag/AgCl reference electrode purged with O₂) and anodic conditions (−0.1 V vs. Ag/AgCl reference electrode purged with H₂) for a long period (4 h). SEM was used to observe the surface morphologies of the samples after corrosion testing. All the TiN-, TiAlN- and CrN-coated SS316L showed a lower CR than the uncoated SS316L. While the corrosion performance of the coatings was dependent on the cathodic and anodic conditions, the CrN coating exhibited a higher (in the anodic environment) or similar (in the cathodic environment) corrosion resistance to the uncoated SS316L. Thus, the CrN-coated SS316L could potentially be used as a bipolar plate material in the PEM fuel cell environment. Although the EBPVD process greatly reduced number of pinholes in the coatings compared to other plasma enhanced reactive evaporations, future research efforts should be directed to eliminate the pinholes in the coatings for long-term durability in fuel cell applications.     

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.     

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.     

Electrodeposition of conductive PAMT/PPY bilayer composite coatings on 316L stainless steel plate for PEMFC application

Stainless steel fulfills most of the requirements as bipolar plates in Proton Exchange Membrane Fuel Cell. However, it undergoes severe corrosion in fuel cell operating condition. This can be resolved by coating the stainless steel with corrosion resistive conducting polymers. In this study, homogeneous and adherent conductive Poly(2-amino-5-mercapto-1,3,4- thiadiazole)/Polypyrrole (PAMT/PPY) mono and bilayer polymer composite coatings are electrosynthesized on 316L SS in 0.5 M H₂SO₄ by cyclic voltammetry and chronopotentiometry. The hydrophobicity and surface morphology of the coatings are analyzed by contact angle and scanning electron microscopy respectively. The polymer coatings are evaluated in 0.5 M H₂SO₄ medium by potentiodynamic polarization and impedance techniques at 25 °C. The polarization results reveal that PAMT on PPY composite coating shifts the E_corr of the 316L SS towards noble direction. The EIS study reveals that the R_f value of PAMT on PPY coating is significantly higher by three orders (x10³ Ωcm²) of magnitude than uncoated 316L SS. The corrosion performance of the coatings in simulated PEMFC environment is investigated by potentiodynamic and potentiostatic studies. Results show that the PAMT on PPY and PPY on PAMT bilayer coatings are stable and increased the corrosion potential by about 410–470 mV and 275–310 mV (SCE) in simulated cathodic and anodic conditions respectively. This investigation reports that the PAMT on PPY bilayer coating is serving as a good physical barrier and protecting the 316L SS against corrosion in PEMFC environment.     

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.     

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.     

SnO2:F coated austenite stainless steels for PEM fuel cell bipolar plates

Austenite stainless steels (316L, 317L, and 349™) have been coated with 0.6 μm thick SnO₂:F by low-pressure chemical vapor deposition and investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) environments. The results showed that substrate steel has a significant influence on the behavior of the coating. Coated 316L showed a steadily increasing anodic current in PEMFC environments, indicating that it is not suitable for this alloy/coating combination. Coated 349™ showed a cathodic current in the PEMFC anode environment, demonstrating its stability in the PEMFC cathode environment. Coated 317L exhibited a stable anodic current after a current peak (at ca. 14 min) in the PEMFC anode environment, and showed an extremely stable low current in PEMFC cathode environment, suggesting the possibility of using SnO₂:F coated 317L for PEMFC bipolar plate applications.     

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.     

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.     

Electrochemical behavior of surface treated metal bipolar plates used in passive direct methanol fuel cell

Corrosion resistance performance of SS316L treated by passivation solution was investigated in a simulated environment of the passive direct methanol fuel cell (DMFC). Electrochemical impedance spectroscopic (EIS) test showed that polarization resistance of untreated and treated SS316L were 1191 Ω cm² and 9335 Ω cm², respectively. The above result agreed with the Tafel slope analysis of potentiodynamic polarization curves. Comparing the untreated and treated SS316L in the simulated environment of DMFC anode working conditions, it was observed that the corrosion current density of treated SS316L as estimated by 4000 s potentiostatic test reduced from 38.7 μA cm⁻² to 0.297 μA cm⁻², meanwhile, the current densities of untreated and treated SS316L in cathode working conditions were 3.87 μA cm⁻² and 0.223 μA cm⁻², respectively. It indicated that the treated SS316L should be suitable in both anode and cathode environment of passive DMFCs. The treated SS316L bipolar plates have been assembled in a passive single fuel cell. A peak power density of 1.18 mW cm⁻² was achieved with 1 M methanol at ambient temperature.     

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.     

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.     

(Titanium,chromium) nitride coatings for bipolar plate of polymer electrolyte membrane fuel cell

(Titanium, chromium) nitride [(Ti,Cr)N] coatings are synthesized on a 316L stainless-steel substrate by inductively-coupled, plasma-assisted, reactive direct current magnetron sputtering. The chemical and electrical properties of the coating are investigated from the viewpoint of it application to bipolar plates. Nanocrystallized Cr–Ti films are formed in the absence of nitrogen gas, while a hexagonal β-(Ti,Cr)₂N phase is observed at N₂ = 1.2 sccm. Well-crystallized (Ti,Cr)N films are obtained at N₂ > 2.0 sccm. The corrosion resistance of the coating is examined by potentiodynamic and potentiostatic tests in 0.05 M H₂SO₄ + 0.2 ppm HF solution at 80 °C, which simulates the operation conditions of a polymer electrolyte membrane fuel cell. The Davies method is used to measure the interfacial contact resistance between the sample and carbon paper. The (Ti,Cr)N coating exhibits the highest corrosion potential and lowest current density. In a cathode environment, the corrosion potential and current density are 0.33 V (vs. SCE) and <5 × 10⁻⁷ A cm⁻² (at 0.6 V), respectively. In an anode environment the corresponding values are 0.16 V and <−5 × 10⁻⁸ A cm⁻² at −0.1 V. The (Ti,Cr)N coatings exhibit excellent stability during potentiostatic polarization tests in both anode and cathode environments. The interfacial contact resistance decreases with deposition of the (Ti,Cr)N film, and a minimum value of 4.5 mΩ cm² is obtained at a compaction force of 150 N cm⁻², which indicates that the formation of oxide films can be successfully prevented by the (Ti,Cr)N film. Analysis with Auger electron spectroscopy reveals that the oxygen content at the surface decreases with increase in the nitrogen content.     

Ni–Cr Co-implanted 316L stainless steel as bipolar plate in polymer electrolyte membrane fuel cells

A Ni–Cr enriched layer about 60 nm thick with improved conductivity is formed on the surface of austenitic stainless steel 316L (SS316L) by ion implantation. The electrochemistry results reveal that a proper Ni–Cr implant fluence can greatly improve the corrosion resistance of SS316L in the simulated PEMFC environment. The samples after the potentiostatic test are also analyzed by XPS and the ICR values are measured. The XPS results indicate that the composition of the passive film change from a mixture of Fe oxides and Cr oxide to a Cr oxide dominated passive film after the potentiostatic test. Hence, the ICR increases after polarization due to depletion of iron in the passive film. Nickel is enriched in the passive film formed in the simulated PEMFC cathode environment after ion implantation thereby providing better conductivity than that formed in the anode one.     

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.     

Corrosion behavior of SS316L in simulated and accelerated PEMFC environments

The electrochemical behavior and change in the passive film formation of SS316L are investigated under polymer electrolyte membrane fuel cell (PEMFC) simulated (pH from 3 to 6 containing F⁻, SO₄²⁻ and Cl⁻ anions) and accelerated conditions (0.5 M and 1 M H₂SO₄ + 2 ppm HF). Potentiodynamic, potentiostatic, and EIS measurements are performed to investigate the electrochemical behavior of the SS316L specimens in both the anode and cathode PEMFC environments. The chemical composition of the passive film, surface topography of the specimens, and degree of metal ion release is characterized by XPS, SEM, and ICP-OES, respectively. The results reveal that the nature of the passive film depends on the pH value, external medium/environment, as well as applied potential during polarization. The corrosion behavior of SS316L is closely related to the chemical composition and structure of the passive film.     

Performance of a high Cr and Ni austenitic stainless steel bipolar plates in proton exchange membrane fuel cell working environments

Electrochemical behavior of a high Cr and Ni austenitic stainless steel (HCN) is investigated and 316L SS in a simulated proton exchange membrane fuel cell environments is also investigated, and interfacial contact resistance (ICR) is measured before and after potentiostatic polarization. Both stainless steels underwent passivation in both anode and cathode environments for proton exchange membrane fuel cell. Passive current density of HCN is lower than that of 316L SS. An increase in ICR between carbon paper and HCN results from passive film formed during the potentiostatic polarization.