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.     

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

Ferrite stainless steels (AISI441, AISI444, and AISI446) were successfully coated with 0.6 μm thick SnO₂:F by low-pressure chemical vapor deposition and investigated in simulated PEMFC environments. The results showed that a SnO₂:F coating enhanced the corrosion resistance of the alloys in PEMFC environments, though the substrate steel has a significant influence on the behavior of the coating. ICP results from the testing solutions indicated that fresh AISI441 had the highest dissolution rates in both environments, and coating with SnO₂:F significantly reduced the dissolution. Coating AISI444 also improved the corrosion resistance. Coating AISI446 steel further improved the already excellent corrosion resistance of this alloy. For coated steels, both potentiostatic polarizations and ICP results showed that the PEMFC cathode environment is much more corrosive than the anode one. More dissolved metallic ions were detected in solutions for PEMFC cathode environment than those in PEMFC anode environment. Sn²⁺ was detected for the coated AISI441 and AISI444 steels but not for coated AISI446, indicating that the corrosion resistance of the substrate has a significant influence on the dissolution of the coating. After coating, the ICR values of the coated steels increased compared to those of the fresh steels. The SnO₂:F coating seems add an additional resistance to the native air-formed film on these stainless steels.     

Anodic behavior of high nitrogen-bearing steels in PEMFC environments

High nitrogen-bearing stainless steels, AISI Type 201 and AL219, were investigated in simulated polymer electrolyte membrane fuel cell (PEMFC) environments to assess the use of these materials in fuel cell bipolar plate applications. Both steels exhibit better corrosion behavior than 316L steel in the same environments. Type 201 steel shows similar but lower interfacial contact resistance (ICR) than 316L, while AL219 steel shows higher ICR than 316L.

X-ray photoelectron spectroscopy (XPS) analysis shows that the air-formed films on Type 201 and AL219 are composed of iron oxides, chromium oxide, and manganese oxide. Iron oxides dominate the composition of the air-formed film, specially the outer layer. Chromium oxide dominates passive films. Surface film thicknesses were estimated. The results suggest that high nitrogen-bearing stainless steels are promising materials for PEMFC bipolar plates.     

Corrosion resistant quaternary Al–Cr–Mo–N coating on type 316L stainless steel bipolar plates for proton exchange membrane fuel cells

Insufficient corrosion resistance, electrical conductivity and wettability of bipolar plates are some of the important issues affecting the performance of hydrogen fuel cells. To address these issues, an amorphous Al–Cr–Mo–N coating is deposited on type 316L stainless steel using direct current (DC) magnetron sputtering. The electrochemical corrosion behaviour is investigated under simulated fuel cell anode (H₂-purging) and cathode (air-purging) environment consisting of 0.5 M H₂SO₄ + 2 ppm NaF at 70 ± 2 °C. The corrosion current density is reduced to 0.02 μA cm⁻² comparable to the commercially used Ta/TaN coatings. The polarization resistance increases by two orders of magnitude and the interfacial contact resistance (ICR) reduces significantly due to the application of the coating. Further, the coating shows better water management due to high hydrophobicity than the bare stainless steel.     

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.     

Corrosion characteristics and fuel cell performance of a cost-effective high Mn–Low Ni austenitic stainless steel as an alternative to SS 316L bipolar plate

In this study, newly developed high manganese (Mn) and low nickel (Ni) austenitic stainless steels were investigated as an alternative to conventionally used SS 316L for bipolar plate applications in proton exchange membrane fuel cells. Systematic studies on the corrosion behavior were carried out in simulated hydrogen and oxygen environments, for both half- and fuel-cell conditions. The Mn-based SS revealed nobler corrosion potential and comparable passive current densities to that of SS 316L. The passive current density of Mn-based SS is well within the DoE 2020 target of <1 μA cm⁻². Though MnSS1 steel has lean Ni content, the addition of Mn and N is beneficial for improving the corrosion performance, which is comparable to SS 316L. The recorded ICR values for Mn SS1 and SS 316L are 234.6 ± 20 and 155 ± 20 mΩ cm² at a compaction force of 140 N cm⁻², respectively. Both the steels do not to meet the DoE ICR target of 10 mΩ cm², which requires conductive coating or improvement in oxide conductivity. The performances of the steels (both Mn-SS and 316L SS) with varying thickness were also investigated in a single fuel cell condition with serpentine flow field design as bipolar plates with varying thickness (10, 5 and 2 mm). A maximum power density of 370 mW cm⁻² was achieved with the Mn-based metallic bipolar plates, whereas SS 316L showed 354 mW cm⁻². By changing the composition of austenitic stainless steel, that is, using Mn SS1 instead of SS 316L the overall fuel cell cost decreases by three times.     

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.     

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.     

Thin chromium nitride PVD coatings on stainless steel for conductive component as bipolar plates of PEM fuel cells: Ex-situ and in-situ performances evaluation

In this paper, two types of chromium PVD coatings (100 nm) have been elaborated on 316L stainless steel (SS) by adjusting the nitrogen flow rate. The first coating is a mixture of Cr₂N and Cr, the second one is a single phase CrN. It is shown that the performances of the material are strongly dependant of the nature of the passive film formed on the chromium nitride layers due to the galvanic coupling between the coating and the substrate. The CrN coated SS shows very good corrosion resistance in simulated PEMFC media. The surface conductivity of the SS is also greatly improved and the CrN coated SS shows an interfacial contact resistance of 10 mΩ cm² at 140 N cm⁻². Five single cells of stainless steel bipolar plates coated with the CrN film were assembled for performance test. This 5 cell stack does not show any mean voltage degradation over 200 h dynamic cycling. Moreover, the performances of the CrN coated SS bipolar plates are very close to the Au-coated SS 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.     

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.     

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.     

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.     

Austenitic stainless steels in high temperature phosphoric acid

Austenite 316 L, 317 L, and 904 L stainless steels were investigated in 98% H₃PO₄ at 170 °C and they experienced passivation regardless of the purged gas. When polarized at 0.1 V (hydrogen) and 0.7 V (air) (phosphoric acid fuel cell (PAFC) environments), currents at the level of mA cm⁻² were observed. Compared to carbon composite under identical conditions, 904 L showed lower currents while 316 L and 317 L showed much higher currents.

X-ray photoelectron spectroscopy (XPS) depth profiles indicated that the surface film of the fresh steels consists of a Fe-oxide-rich outer layer and a Cr-oxide-rich inner layer. After being polarized in the PAFC environments, the Fe-oxide layer was selectively dissolved and Cr-oxide dominated the passive film. Phosphorus was incorporated into the film during the process, thus the chemical composition of the passive film differed from those formed in the polymer electrolyte membrane fuel cell (PEMFC) environments. The thicknesses of the stainless steels in the passive films in PAFC environments were estimated.     

Characterisations of electrospark deposition Stellite 6 alloy coating on 316L sealed valve used in nuclear power plant

Abstract

In nuclear plant the protection of the H₂BO₄ solution seal areas of AISI 316L austenitic steel is accomplished by Stellite 6 plasma cladding layer. Wear defects created in service required the part to be replaced or repaired. No existing repair technologies were practical. Electrospark deposition (ESD) was to repair defects, enabling the parts to be placed back in service. In this paper the authors report the results obtained depositing directly a layer of Stellite 6 alloy onto a 316L austenitic stainless and Stellite 6 plasma cladding layer by using ESD technique. Electrospark deposition can apply metallurgical bonded coatings without the need of post-heat treatment. Structure, hardness, chemical composition and morphology of the ESD coating have been analysed. By electrochemical measurements it is inferred that the corrosion resistance of the ESD coating is comparable to that of the 316L and Stellite 6 plasma cladding layer. The hardness improvement was ascribed to the refine microstructure and the rapid solidification.     

Performance of surface chromizing layer on 316L stainless steel for proton exchange membrane fuel cell bipolar plates

Stainless steels as proton exchange membrane fuel cell bipolar plates have received extensive attention in recent years. The pack chromizing layer was fabricated on 316L stainless steel to improve the corrosion resistance and electrical conductivity. The corrosion properties were investigated in 0.5 M H₂SO₄ + 2 ppm HF solution at 70 °C purged with hydrogen gas and air. Higher electrochemical impedance and more stable passive film were obtained by chromizing the 316L stainless steel. Potentiodynamic polarization results showed the corrosion current densities were reduced to 0.264  μA cm⁻² and 0.222  μA cm⁻² in two simulated operating environments. In addition, the interfacial contact resistance was decreased to 1.4 mΩ⋅cm² under the compaction force of 140 N⋅cm⁻² and maintained at low values after potentiostatic polarization for 4 h. The excellent corrosion and conductive performances could be attributed to the chromium carbides and high alloying element content in chromizing layer.     

杂质氯离子对新型四元硝酸盐腐蚀性的影响

为了探究低氯离子含量（0.01%~0.05%,质量分数）对熔盐与金属材料腐蚀过程的影响,该文采用失重法研究316L不锈钢与氯离子质量分数为0.01%、0.03%、0.05%的混合硝酸盐的腐蚀行为。结果发现,在经过360 h的腐蚀实验后,316L不锈钢在氯离子质量分数为0.03%的熔盐中具有最小的失重量,其为0.4381 mg/cm²。采用SEM、EDS、XRD等方法对316L不锈钢表面形貌进行分析,结果表明,在添加氯离子后不锈钢的腐蚀产物中出现Ca（OH）₂,在Ca（OH）₂的形成过程会消耗氢氧根离子,从而降低了不锈钢失重量。     

Corrosion inhibition of methanol towards stainless steel bipolar plate for direct formic acid fuel cell

The corrosion properties of AISI316L stainless steel (316 L SS) as bipolar plates are investigated under aqueous acid methanol solutions (0.05 M H₂SO₄ + 2 ppm HF + 10 M HCOOH + x M CH₃OH (x = 0, 3, 6 and 9) solutions at 70 °C) to simulate the varied anodic operating conditions of direct formic acid fuel cells (DFAFCs). When the methanol content is higher, the potentiodynamic, potentiostatic polarisation and EIS tests of the 316 L SS bipolar plates all show excellent corrosion resistance. The surface morphology and the glow discharge mass spectrometer (GDMS) illustrate that the surface corrosion on 316 L SS bipolar plates is slowed down when the methanol concentration is increased. These results indicate the methanol plays the role in retarding the corrosion rate of the 316 L SS in simulated DFAFCs anodic operating conditions by restricting the proton conductivity in the test solutions. The sample tested in higher content methanol solution has smoother corroded surface and thinner passivation film, which contributes to a lower interfacial contact resistances (ICR) value.     

Corrosion fatigue behaviour of 317LN austenitic stainless steel in phosphoric acid

The corrosion fatigue crack-growth behaviour of AISI 317LN stainless steel was evaluated in air and in 85% phosphoric acid at 20 °C. Austenitic stainless steels with high molybdenum content have high corrosion resistance and good mechanical properties. However, this increase in the molybdenum content and other elements such as nitrogen can also modify the microstructure. This leads to a modification of its mechanical properties. The corrosion fatigue crack-growth rate was higher in phosphoric acid immersion than in air. Austenitic stainless steels with a fully austenitic microstructure were more ductile, tough, and behave better against corrosion fatigue. The higher resistance to corrosion fatigue was directly associated to its higher resistance to corrosion.     

Arc ion plated Cr/CrN/Cr multilayers on 316L stainless steel as bipolar plates for polymer electrolyte membrane fuel cells

Arc ion plating (AIP) is applied to coat sandwich-like Cr/CrN/Cr multilayers on stainless steel 316L (SS316L) as bipolar plates for polymer electrolyte membrane fuel cell (PEMFC). Phase structure, hardness, adhesion property, interfacial contact resistance (ICR) between bipolar plates and carbon papers, and electrochemical corrosion property in the simulated PEMFC conditions are investigated. Cr phase with crystal plane of (1 1 0), (2 1 1), (3 2 2), and CrN phase with (3 2 1) are observed in the multilayer. The coating is found smooth, continuous and dense in cross-sectional observation by SEM, and the sandwiched structure of the coating is also confirmed by EDX results. Scratch tests show that the multilayer exhibits strong adhesion strength with steel substrate, which is beneficial to prevent layers from peeling off mechanically. After the coating treatment, the performance of the bipolar plate is greatly improved. Knoop hardness of the bipolar plates increases from 324 HK to 692 HK. The ICR decreases by one order of magnitude; furthermore, the corrosion resistance was also enhanced. Our analysis indicates that the improvement is attributed to high adhesion force of the smooth and dense coating and the synergistic function of Cr/CrN/Cr multilayer structure.