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.     

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.     

Catalyst layer-free carbon-coated steel—An easy route to bipolar plates of polymer electrolyte membrane fuel cells: Characterization on structure and electrochemistry

Stainless steel coated with carbon by CVD process has been evaluated as a low-cost and small-volume substitute for graphite bipolar plate in polymer electrolyte membrane fuel cell (PEMFC). Carbon film was grown at 690–930 °C under gas-mixture of C₂H₂–H₂. Scanning electron microscopy and X-ray diffractometry were used to characterize surface morphology and crystal structure of resultant carbon films, which were found to depend much on reaction temperature. Interfacial contact resistance (ICR), hydrophobicity and chemical stability of obtained specimens were measured to compare with commercial highly oriented pyrolytic graphite (HOPG). All carbon films investigated in this study show improved ICR and hydrophobicity of SUS304 substrate to the level of HOPG. Amorphous carbon layer with continuous film structure prepared at 810 °C shows the best protection of SUS304 substrate against the attack of H_(aq)⁺ (anodic side) and the best resistance of the coated carbon from gasification (cathodic side) in the simulated PEMFC environment.     

Effect of pH value on corrosion resistance and surface conductivity of plasma‐nitrided 304L bipolar plate for PEMFC

Low temperature plasma nitriding is developed to meet the requirements for corrosion resistance and interfacial contact resistance (ICR) of stainless steel 304L as the bipolar plate for PEMFC. A dense and supersaturated‐nitrogen nitrided layer has formed on the surface of the stainless steel 304L. Electrochemical behavior for the untreated and plasma‐nitrided 304L was measured in H₂SO₄ (pH=1–5)+2 ppm F^? simulating PEMFC environment, and the ICR was evaluated before and after corrosion tests. The experimental results have shown that the ICR for the plasma nitrided 304L is lower than the requirement of U.S. DOE (<10 mΩ cm² to 2010). Corrosion resistance and the ICR at the compaction force of 150–200 N cm^?2 increase with increasing pH value for the untreated and plasma‐nitrided 304L. The passive current densities for the untreated and plasma‐nitrided 304L are all lower than 16 µA cm^?2. The ICR between passive film and carbon paper are increased markedly because of passive film formed on the surface of both studied 304L. However, the passive current density and the ICR are lower for the plasma nitrided 304L than those for the untreated one at the given pH value, which results from the different composition of the stable passive film formed on the surface. The low temperature plasma nitriding provides a promising method for 304L using as bipolar plate for PEMFC. Further research is needed to evaluate the long‐term stability of passive film and the performance of single fuel cell. Copyright © 2010 John Wiley & Sons, Ltd.     

Improvement of corrosion resistance and electrical conductivity of 304 stainless steel using close field unbalanced magnetron sputtered carbon film

Carbon film has been deposited on 304 stainless steel (SS304) using close field unbalanced magnetron sputter ion plating (CFUBMSIP) to improve the corrosion resistance and electrical conductivity of SS304 acting as bipolar plates for proton exchange membrane fuel cells (PEMFCs). The corrosion resistance, interfacial contact resistance (ICR), surface morphology and contact angle with water of the bare and carbon-coated SS304 are investigated. The carbon-coated SS304 shows good corrosion resistance in the simulated cathode and anode PEMFC environment. The ICR between the carbon-coated SS304 and the carbon paper is 8.28-2.59 mΩ cm² under compaction forces between 75 and 360 N cm⁻². The contact angle of the carbon-coated SS304 with water is 88.6°, which is beneficial to water management in the fuel cell stack. These results indicate that the carbon-coated SS304 exhibits high corrosion resistance, low ICR and hydrophobicity and is a promising candidate for bipolar plates.     

Electrodeposition of ruthenium oxide on ferritic stainless steel bipolar plate for polymer electrolyte membrane fuel cells

The effect of RuO₂ electrodeposition on ferritic stainless steel as a bipolar plate is evaluated in terms of the surface morphology, interfacial contact resistance (ICR), potentiostatic polarization, contact angle, and X-ray photoelectron spectroscopy. The surface morphology of deposited RuO₂ is greatly stabilized by addition of HNO₃ in 10 mM RuCl₃·xH₂O solution. The RuO₂-deposition on stainless steel shows a high contact angle indicating the high surface energy and hydrophobic characteristics. The ICR measurement indicates that the deposition of conductive RuO₂ on stainless steel is very effective in decreasing ICR value. Moreover, after potentiostatic polarization, the ICR value shows only 2.4 and 2.2 mΩ cm² at 150 N/cm² under air and H₂ purged environments, respectively. In electrochemical test, even though the current density of RuO₂-deposited stainless steel is slightly higher than that of bare stainless steel, it is acceptable value for the relevant DOE 2015 target for metallic bipolar plates (less than 1 μA/cm²). Because the RuO₂-deposition on stainless steel shows a low ICR value and good corrosion resistance and high contact angle, the RuO₂-deposition is a sufficiently feasible method for the bipolar plate material of PEMFC.     

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.     

Synthesis of mesoporous carbon-silica-polyaniline and nitrogen-containing carbon-silica films and their corrosion behavior in simulated proton exchange membrane fuel cells environment

In this study, polyaniline is deposited onto mesoporous carbon-silica-coated 304 stainless steel using electropolymerization method. Variation of the electropolymerization time and applied potential can affect the growth of polyaniline, and lead to different structural and electrochemical properties of the films. Nitrogen-containing groups are successfully introduced onto the mesoporous carbon-silica film by pyrolyzing treatment under N₂ atmosphere and the electrical conductivity is improved observably compared with the carbon-silica film. The electrochemical properties of the mesoporous carbon-silica-polyaniline films and nitrogen-containing carbon-silica composite films are examined by using potentiodynamic polarization, potentiostatic polarization and electrochemical impedance spectroscopy. The corrosion tests in 0.5 M H₂SO₄ system display that the carbon-silica-polyaniline films show the optimal protective performance. However, according to potentiostatic polarization process, nitrogen-containing carbon-silica film with a water contact angle 95° is extremely stable and better for the protection of stainless steel in simulated fuel cell environment compared to carbon-silica-polyaniline film. Therefore, the nitrogen-containing carbon-silica-coated 304 stainless steel is a promising candidate for bipolar plate materials in PEMFCs.     

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.     

Carbon film-coated 304 stainless steel as PEMFC bipolar plate

Carbon film-coated stainless steel (CFCSS) has been evaluated as a low-cost and small-volume substitute for graphite bipolar plate in polymer electrolyte membrane fuel cell (PEMFC). In the present work, AISI 304 stainless steel (304SS) plate was coated with nickel layer to catalyze carbon deposits at 680°C under C₂H₂/H₂ mixed gas atmosphere. Surface morphologies of carbon deposits exhibited strong dependence on the concentration of carbonaceous gas and a continuous carbon film with compact structure was obtained at 680 °C under C₂H₂/H₂ mixed gas ratio of 0.45. Systematic analyses indicated that the carbon film was composed of a highly ordered graphite layer and a surface layer with disarranged graphite structure. Both corrosion endurance tests and PEMFC operations showed that the carbon film revealed excellent chemical stability similar to high-purity graphite plate, which successfully protected 304SS substrate against the corrosive environment in PEMFC. We therefore predict CFCSS plates may practically replace commercial graphite plates in the application of PEMFC.     

Niobium diffusion modified austenitic stainless steel bipolar plate for direct methanol fuel cell

An austenitic stainless steel with a niobium diffusion protective layer is evaluated for bipolar plate of direct methanol fuel cell (DMFC). Corrosion resistance of niobium diffusion modified AISI 304 stainless steel (niobized 304 SS) is investigated in simulated DMFC cathodic environment (0.5 M H₂SO₄ + 2 ppm HF + 0.1 M methanol solution at 50 °C) and anodic environment (0.5 M H₂SO₄ + 2 ppm HF + (1 M, 10 M and 20 M) methanol solution at 50 °C), respectively. Potentiodynamic, potentiostatic as well as electrochemical impedance spectroscopy tests show that, comparing with a bare 304 SS, the corrosion current density of niobized 304 SS is reduced greatly while the polarization resistance is raised in the simulated DMFC cathodic environment. Corrosion tests in the simulated anodic environment are applied to examine the effect of methanol on the corrosion behaviour of niobized 304 SS. It is interesting to find that the niobized 304 SS shows better corrosion resistance in the higher methanol concentration solutions.     

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.     

Investigation of acidity on corrosion behavior and surface properties of SS304 in simulated PEMFC cathode environments

This study presents the influence of acidity on the corrosion performance and surface properties of AISI 304 stainless steel (SS304) in the simulated cathode condition of proton exchange membrane fuel cells (PEMFC) with various concentrations of H₂SO₄. The electrochemical tests indicate that the corrosion resistance of SS304 samples decreases gradually with the solution acidity ascending, but the stable current densities (0.043–0.547 μA cm^?2) in the simulated solutions after polarization (0.6 V, 5 h) are all lower than that of the relevant DOE 2025 target (i_corr < 1 μA cm^?2). Obvious pitting corrosion occur in the solutions with H₂SO₄ concentration higher than 10^?3 M. The surface wettability and interfacial contact resistance (ICR) of the potentiostatically polarized SS304 show an upward trend with the solution acidity increasing, and whether the SS304 samples are polarized or not, their ICR (0.274–1.232 Ω cm²) is far higher than the latest DOE 2025 technical target (<0.01 Ω cm²). The results reveal that surface modification is indispensable for SS304 as bipolar plates, and more attention should be paid to possessing high and stable pitting resistance, hydrophobicity, and interfacial conductivity in an acid environment.     

Coated 316L stainless steel with CrxN film as bipolar plate for PEMFC prepared by pulsed bias arc ion plating

Three different kinds of Cr_xN films on 316L stainless steels were prepared by pulsed bias arc ion plating as bipolar plates for proton exchange membrane fuel cell (PEMFC). The interfacial contact resistance, corrosion resistance and surface energy of the bipolar plate samples were investigated. Among the three samples, the 316L stainless steel coated with Cr_0.49N_0.51 → Cr_0.43N_0.57 gradient film (sample 2) exhibited the best-integrated performance. The contact resistance between sample 2 and Toray carbon paper was 6.9–10.0 mΩ cm² under 0.8–1.2 MPa. The bipolar plate sample also showed improved corrosion resistance in simulated PEMFC environments. Either in the reduction environment or in the oxidation environment 25 °C and 70 °C, the corrosion current densities of sample 2 were about one to two orders of magnitude lower than those of the base metal. In addition, the open circuit corrosion potential of sample 2 was also the highest in 0.5 M H₂SO₄ + 5 ppm F⁻ solution at 25 °C. The treated bipolar plate had high surface energy; and the contact angle of sample 2 with water was about 90°, which is beneficial for water management in fuel cell.     

Corrosion protection of 304 stainless steel bipolar plates using TiC films produced by high-energy micro-arc alloying process

Metallic bipolar plates look promising for the replacement of graphite due to higher mechanical strength, better durability to shocks and vibration, no gas permeability, acceptable material cost and superior applicability to mass production. However, the corrosion and passivation of metals in environments of proton exchange membrane fuel cell (PEMFC) cause considerable power degradation. Great attempts were conducted to improve the corrosion resistance of metals while keeping low contact resistance. In this paper, a simple, novel and cost-effective high-energy micro-arc alloying process was employed to prepare compact titanium carbide as coatings for the type 304 stainless steel bipolar plates with a metallurgical bonding between the coating and substrate. It was found that TiC coating increased the corrosion potential of the bare steel in 1 M H₂SO₄ solution at room temperature by more than 200 mV, and decreased significantly its corrosion current density from 8.3 μA cm⁻² for the bare steel to 0.034 μA cm⁻² for the TiC-coated steel. No obvious degradation was observed for the TiC coatings after 30-day exposure in solution.     

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.     

An investigation of Zr-based bulk metallic glasses as bipolar plates for proton exchange membrane fuel cells

The electrochemical properties and interfacial contact resistance (ICR) of four Zr-based bulk metallic glasses with different compositions are evaluated for PEMFC applications. Based on the results and market demands, the corrosion behavior of the Zr_41·2Ti_13·8Cu_12·5Ni₁₀Be_22.5 (numbers indicate at.%) BMG and 304 stainless steel (SS304) in accelerated simulated anode and cathode environments, such as 0.5 M H₂SO₄ and 2 ppm HF solutions bubbled with pure hydrogen and air at 80 °C, respectively, is further investigated through potentiodynamic polarization, potentiostatic polarization, and electrochemical impedance spectroscopy. The performance tests of the single cell with the Zr-based BMG as BPPs are conducted and the maximum power density of the single cell has exceeded 470 mW/cm². The combination of these results and other properties demonstrate that the Zr-based BMG can be used as the anode or cathode material for metallic bipolar plates.     

Inductively coupled plasma nitriding of chromium electroplated AISI 316L stainless steel for PEMFC bipolar plate

Chromium electroplated AISI 316L stainless steel was nitrided using inductively coupled plasma (ICP) for application in the bipolar plate of a polymer electrolyte membrane fuel cell (PEMFC). A continuous and thin chromium nitride layer was formed at the surface of the samples after ICP nitriding for 2 h at 400 °C. The interfacial contact resistance (ICR) and corrosion resistance in simulated PEMFC operating conditions were higher than the required values, while they varied with the applied dc bias voltage during the nitriding process. The ICR value decreased with an increase in bias voltage. Potentiodynamic polarization measurements showed that all of the nitrided samples had excellent corrosion resistance with a current density of ∼10⁻⁷ A cm⁻² at the cathode. It was also found that the oxygen content at the surface was not increased after the corrosion test. X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), and Auger electron spectroscopy (AES) were used to analyze the effect of plasma nitriding.     

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.     

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.