Corrosion and Interfacial Contact Resistance of NiTi Alloy as a Promising Bipolar Plate for PEMFC.

Titanium (Ti) is generally considered as an ideal bipolar plate (BPP) material because of its excellent corrosion resistance, good machinability and lightweight nature. However, the easy-passivation property, which leads to increased interfacial contact resistance (ICR) and subsequently decreased cell performance, limits its large-scale commercial application in proton exchange membrane fuel cells (PEMFCs). In this paper, we proposed a NiTi alloy prepared by suction casting as a promising bipolar plate for PEMFCs. This NiTi alloy exhibits significantly decreased ICR values (16.8 mΩ cm2 at 1.4 MPa) compared with pure Ti (88.6 mΩ cm2 at 1.4 MPa), along with enhanced corrosion resistance compared with pure nickel (Ni). The superior corrosion resistance of NiTi alloy is accredited to the nobler open circuit potential and corrosion potential, coupled with low corrosion current densities and passive current densities. The improved ICR can be interpreted by the existence of high-proportioned metallic Ni in the passive film, which contributes to the reduced capacitance characteristic of the passive film (compared with Ti) and enhances charge conduction. This work provides a feasible option to ameliorate BPP material that may have desirable corrosion resistance and ICR.

Comparison of Magnetron-Sputtered and Cathodic Arc-Deposited Ti and Cr Thin Films on Stainless Steel for Bipolar Plates.

In this work, the potential of magnetron sputtering, as well as cathodic arc evaporation, is investigated with regard to its suitability as a bipolar plate coating of a PEM fuel cell. For this purpose, Cr and Ti thin films were deposited onto a 0.1 mm SS316L by varying the power and bias voltage. The surface structure and thickness of the coatings are examined via SEM and tactile profilometry. Moreover, the coating variants are compared with each other based on the electrical and electrochemical properties relevant to bipolar plates. The sputtered Cr thin films achieve the lowest contact resistance values and exhibit a columnar structure with a smooth surface. Regarding the electrochemical properties, titanium deposited via cathodic arc evaporation has a low current density in the passive region and high breakthrough potential. All in all, both deposition techniques have their individual advantages for the preparation of bipolar plates' coatings. However, Ti thin films prepared via cathodic arc seem to be the most suitable option due to the combination of a high deposition rate, a low cost and good coating properties.

Investigation of the Performance of Hastelloy X as Potential Bipolar Plate Materials in Proton Exchange Membrane Fuel Cells.

The phase, mechanical properties, corrosion resistance, hydrophobicity, and interfacial contact resistance of Hastelloy X were investigated to evaluate its performance in proton exchange membrane fuel cells (PEMFCs). For comparison, the corresponding performance of 304 stainless steel (304SS) was also tested. Hastelloy X exhibited a single-phase face-centered cubic structure with a yield strength of 445.5 MPa and a hardness of 262.7 HV. Both Hastelloy X and 304SS exhibited poor hydrophobicity because the water contact angles were all below 80°. In a simulated PEMFC working environment (0.5 M H2SO4 + 2 ppm HF, 80 °C, H2), Hastelloy X exhibited better corrosion resistance than 304SS. At 140 N·cm-2, the interfacial contact resistance of Hastelloy X can reach as low as 7.4 mΩ·cm2. Considering its overall performance, Hastelloy X has better potential application than 304SS as bipolar plate material in PEMFCs.

Ion Implantation Combined with Heat Treatment Enables Excellent Conductivity and Corrosion Resistance of Stainless Steel Bipolar Plates for Hydrogen Fuel Cells.

316 L stainless steel is an ideal bipolar plate material for a proton exchange membrane fuel cell (PEMFC). However, the thickening of the passivation film on the stainless steel surface and the dissolution of corrosive ions during operation will affect the durability of the PEMFC. Herein, a heterogeneous layer is prepared on the surface of 316 L stainless steel through dual ion implantation of molybdenum ion and carbon ion combined with heat treatment to promote the corrosion resistance and conductivity of the bipolar plate. The ion implantation technique resulted in a uniform distribution of Mo and C elements on the surface of 316 L stainless steel, with a modified layer depth of about 70-80 nm. The electrical conductivity of the ion implanted samples was significantly improved, and the interfacial contact resistance was reduced from 464.25 mΩ × cm2 to 42.49 mΩ × cm2. Heat treatment enhances the surface homogenization, repairs the defects of irradiation damage, and improves the corrosion resistance of stainless steel. The corrosion current density of (Mo+C)-600 samples decreased from 1.21 × 10-8 A/cm2 to 2.95 × 10-9 A/cm2 under the long-term corrosion condition of 4 h. These results can provide guidance for the modification of stainless steel bipolar plates.

Investigation on the physical and electrochemical properties of typical Ni-based alloys used for the bipolar plates of proton exchange membrane fuel cells.

The phase, mechanical properties, corrosion resistance, hydrophobicity, and interface contact resistance of three typical Ni-based alloys (Hastelloy B, Hastelloy C-276, and Monel 400) and 304 stainless steels were experimentally studied to evaluate their service performances as bipolar plate materials of proton exchange membrane fuel cells. All four alloys exhibit single-phase face-centered cubic structure, high strength, good ductility, and high hardness. Hastelloy C-276 has the best ductility with an uniform elongation of 72.5% and highest hardness of 363.7 HV. Hastelloy B has the highest ultimate tensile strength of 913.6 MPa. The hydrophobicity of all four alloys is not good, although Monel 400 has the highest water contact angle of 84.2°. Hastelloy B, Hastelloy C-276, and 304 stainless steel exhibit unsatisfying corrosion resistance in a simulated acidic work environment of proton exchange membrane fuel cell (0.5 M H2SO4+2 ppm HF, 80 °C, H2) and high interface contact resistance. By contrast, Monel 400 demonstrates excellent corrosion resistance with a corrosion current density of 5.9 × 10-7 A cm-2 and a low interface contact resistance of 7.2 mΩ cm2 at 140 N/cm2. In terms of comprehensive performance, Monel 400 is the best uncoated material for the bipolar plates of proton exchange membrane fuel cells among typical Ni-based alloys.

Improvement in Corrosion Resistance and Interfacial Contact Resistance Properties of 316L Stainless Steel by Coating with Cr, Ti Co-Doped Amorphous Carbon Films in the Environment of the PEMFCs.

In order to obtain films with high corrosion resistance and excellent interfacial contact resistance (ICR) on 316L stainless steel used for bipolar plates in proton-exchange membrane fuel cells (PEMFCs), Cr, Ti co-doped amorphous carbon films were prepared on 316L stainless steel. The preparation method for the coating was magnetron sputtering. The doping amount of the Ti element was controlled by a Cr target and a Ti target current. The change in the structure and properties of the coating after the change from Cr single-element doping to Cr and Ti co-doping was studied. The change rule of the structure and properties of the coating from Cr single-element doping to Cr and Ti co-doping was studied. An increase in the Ti content led to a decreased grain boundary, a flatter surface, and a higher sp2-hybridized carbon content. TiC and CrC nanocrystals were formed in the amorphous carbon structure together. The amorphous carbon films doped with Cr and Ti simultaneously achieved a low ICR and high corrosion resistance compared with single-Cr-doped amorphous carbon. The enhanced corrosion resistance was attributed to the decreasing grain boundary, the formation of the TiC crystal structure, and the smaller grain size. The best performance was obtained at a Ti target current of 2A. Compared with bare 316L stainless steel, the corrosion resistance of Cr, Ti co-doped amorphous carbon (Icorr = 5.7 × 10-8 A/cm2, Ti-2 sample) was greatly improved. Because Ti doping increased the content of sp2-hybridized carbon in the coating, the contact resistance of the coating decreased. Moreover, the interfacial contact resistance was 3.1 mΩ·cm2 in the Ti-2 sample, much lower than that of bare 316L stainless steel. After the potentiostatic polarization test, the coating still had excellent conductivity.

Au-TiO2/Ti Hybrid Coating as a Liquid and Gas Diffusion Layer with Improved Performance and Stability in Proton Exchange Membrane Water Electrolyzer.

The liquid and gas diffusion layer is a key component of proton exchange membrane water electrolyzer (PEMWE), and its interfacial contact resistance (ICR) and corrosion resistance have a great impact on the performance and durability of PEMWE. In this work, a novel hybrid coating with Au contacts discontinuously embedded in a titanium oxidized layer was constructed on a Ti felt via facile electrochemical metallizing and followed by a pre-oxidization process. The physicochemical characterizations, such as scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction results confirmed that the distribution and morphology of the Au contacts could be regulated with the electrical pulse time, and a hybrid coating (Au-TiO2/Ti) was eventually achieved after the long-term stability test under anode environment. At the compaction force of 140 N cm-2, the ICR was reduced from 19.7 mΩ cm2 of the P-Ti to 4.2 mΩ cm2 of the Au-TiO2/Ti. The corrosion current density at 1.8 V (RHE) is 0.689 µA cm-2. Both the ICR and corrosion resistance results showed that the prepared protective coating could provide comparable ICR and corrosion resistance to a dense Au coating.

Direct Wet-Spun Single-Walled Carbon Nanotubes-Based p-n Segmented Filaments toward Wearable Thermoelectric Textiles.

Three-dimensional thermoelectric (TE) textiles (TETs) fabricated with TE filaments (TEFs) possess merits over other types such as thickness-direction thermal energy harvesting and excellent conformability with dynamic body curves, revealing the prospect of generating electricity for on-body application. Nonetheless, there is still a lack of a costless but scalable method to automatically and seamlessly produce in-series interconnected p-n segmented TEFs with high TE properties via conventional fiber spinning processes. Here, we developed an alternate wet-spinning strategy to continuously manufacture single-walled carbon nanotube-based p-n segmented TEFs at large scale. The TEF with high electrical conductivity (400-800 S cm-1) displays a low contact resistivity of 189.8 µΩ cm2 between the segments and interelectrode, showing 2 orders of magnitude smaller than that reported in the literature. More importantly, the power factors of p-type and n-type segments are 26.25 and 17.14 µW m-1 K-2, respectively, which are 3 and 4 orders of magnitude higher than those of advanced studies. We finally embroidered it into spacer fabric to fabricate a wearable TET, demonstrating an output power density of 501 nW m-2 at ΔT = 27.7 K. The methodology can inspire the development of fiber-based electronics such as wearable TEs and diodes and so forth.

Study on Corrosion Resistance and Conductivity of TiMoN Coatings with Different Mo Contents under Simulated PEMFC Cathode Environment.

TiMoN coatings with different Mo contents on a SS316L substrate are deposited by using closed field unbalanced magnetron sputtering ion plating (CFUMSIP) technology to enhance the corrosion resistance and durability of stainless steel (SS) bipolar plates (BPs) in proton exchange membrane fuel cell (PEMFC) during the start-up/shut-down process. The electrochemical test results illustrate that TiMoN-4A coating has extremely good corrosion resistance compared to other coatings. The potentiostat polarization (+0.6 VSCE) tests indicate that the corrosion current density (Icorr) of TiMoN-4A coating is 5.22 × 10-7A cm-2, which meets the department of energy 2020 targets (DOE, ≤1 × 10-6 A cm-2). Otherwise, TiMoN-4A coating also exhibits the best corrosion resistance and stability in potentiostatic polarization, electrochemical impedance spectroscopy (EIS), and high potential (+1.2VSCE) polarization tests. The interfacial contact resistance (ICR) measurement results show that TiMoN-4A coating has the minimum ICR of 9.19 mΩ·cm2, which meets the DOE 2020 targets (≤10 mΩ·cm2).

Vertical-Graphene-Reinforced Titanium Alloy Bipolar Plates in Fuel Cells.

The bipolar plate (BP) serves as one of the crucial components in proton exchange membrane fuel cells (PEMFCs). Among BP materials, metallic BPs are widely employed due to their outstanding comprehensive properties. However, the interfacial contact resistance (ICR) between BP and gas diffusion layer together with corrosion of metallic BP under acidic operating conditions degrades the performance and stability of PEMFCs. Herein, an approach is proposed for the surface reinforcement of titanium (Ti) alloy BPs, relying on a directly grown vertical graphene (VG) coating via the plasma-enhanced chemical vapor deposition method. Compared with bare Ti alloy, the corrosion rate of VG-coated Ti alloy reduces by 1-2 orders of magnitude in the simulated PEMFC operating environments and ICR decreases by ≈100 times, while its thermal conductivity improves by ≈20% and water contact angle increases by 68.1°. The results can be interpreted that the unique structure of VG enables excellent electrical and thermal conduction in PEMFCs, and the highly hydrophobic VG coating suppresses the penetration of corrosive liquid as well as contributing to water management. This study opens a new opportunity to reinforce metallic surfaces by the robust and versatile VG coating for high-performance electrodes used in energy and catalyst applications.

Collective Enhancements on Thermal-Electrical and Mechanical Properties of Graphite-Based Composite Bipolar Plates through the Coupled Manipulations of Molding and Impregnation Pressures.

The performance and durability of proton exchange fuel cells (PEMFCs) are greatly affected by the bipolar plate (BP). In this paper, the thermal and electrical conductivities and mechanical property of graphite filled with resin composite BPs were collectively enhanced through the effectively coupled manipulations of molding pressure and impregnation pressure. The microstructures show that the resin tends to distribute at the top region of the rib under high impregnation pressure. The thermal and electrical conductivities of the pure expanded graphite BP is well reserved in the composite BPs under high molding pressure, which can facilitate the heat transfer and electron conduction in the PEMFCs. The relative density and compressive strength of composite BPs were greatly enhanced by the impregnation of resin compared to the expanded graphite under high molding pressure without the impregnation of resin (HU-BP). The maximum thermal conductivity, compressive strength, and minimum interfacial contact resistance (ICR) are collectively achieved in the HL-BP. The enhanced thermal-electrical and mechanical properties could be mainly attributed to the well-reserved continuous networks of graphite in the composite BPs. The findings in this paper are expected to synergetically improve the thermal, electrical, and mechanical properties of composite BPs through coupled manipulations of the molding and impregnation pressures, which in turn enhances the power density and durability of PEMFCs.

Detection and Analysis of Corrosion and Contact Resistance Faults of TiN and CrN Coatings on 410 Stainless Steel as Bipolar Plates in PEM Fuel Cells.

Bipolar Plates (BPPs) are the most crucial component of the Polymer Electrolyte Membrane (PEM) fuel cell system. To improve fuel cell stack performance and lifetime, corrosion resistance and Interfacial Contact Resistance (ICR) enhancement are two essential factors for metallic BPPs. One of the most effective methods to achieve this purpose is adding a thin solid film of conductive coating on the surfaces of these plates. In the present study, 410 Stainless Steel (SS) was selected as a metallic bipolar plate. The coating process was performed using titanium nitride and chromium nitride by the Cathodic Arc Evaporation (CAE) method. The main focus of this study was to select the best coating among CrN and TiN on the proposed alloy as a substrate of PEM fuel cells through the comparison technique with simultaneous consideration of corrosion resistance and ICR value. After verifying the TiN and CrN coating compound, the electrochemical assessment was conducted by the potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) tests. The results of PDP show that all coated samples have an increase in the polarization resistance (Rp) values (ranging from 410.2 to 690.6 Ω·cm2) compared to substrate 410 SS (230.1 Ω·cm2). Corrosion rate values for bare 410 SS, CrN, and TiN coatings were measured as 0.096, 0.032, and 0.060 mpy, respectively. Facilities for X-ray Diffraction (XRD), Scanning Electron Microscope (FE-SEM, TeScan-Mira III model and made in the Czech Republic), and Energy Dispersive X-ray Spectroscopy (EDXS) were utilized to perform phase, corrosion behavior, and microstructure analysis. Furthermore, ICR tests were performed on both coated and uncoated specimens. However, the ICR of the coated samples increased slightly compared to uncoated samples. Finally, according to corrosion performance results and ICR values, it can be concluded that the CrN layer is a suitable choice for deposition on 410 SS with the aim of being used in a BPP fuel cell system.

Metallic Material Selection and Prospective Surface Treatments for Proton Exchange Membrane Fuel Cell Bipolar Plates-A Review.

The aim of this review is to summarize the possibilities of replacing graphite bipolar plates in fuel-cells. The review is mostly focused on metallic bipolar plates, which benefit from many properties required for fuel cells, viz. good mechanical properties, thermal and electrical conductivity, availability, and others. The main disadvantage of metals is that their corrosion resistance in the fuel-cell environment originates from the formation of a passive layer, which significantly increases interfacial contact resistance. Suitable coating systems prepared by a proper deposition method are eventually able to compensate for this disadvantage and make the replacement of graphite bipolar plates possible. This review compares coatings, materials, and deposition methods based on electrochemical measurements and contact resistance properties with respect to achieving appropriate parameters established by the DOE as objectives for 2020. An extraordinary number of studies have been performed, but only a minority of them provided promising results. One of these is the nanocrystalline ß-Nb2N coating on AISI 430, prepared by the disproportionation reaction of Nb(IV) in molten salt, which satisfied the DOE 2020 objectives in terms of corrosion resistance and interfacial contact resistance. From other studies, TiN, CrN, NbC, TiC, or amorphous carbon-based coatings seem to be promising. This paper is novel in extracting important aspects for future studies and methods for testing the properties of metallic materials and factors affecting monitoring characteristics and parameters.

Impact of Film Thickness on Defects and the Graphitization of Nanothin Carbon Coatings Used for Metallic Bipolar Plates in Proton Exchange Membrane Fuel Cells.

Metallic bipolar plates (BPPs) are considered promising alternatives to traditional graphite BPPs used in proton exchange membrane fuel cells (PEMFCs). Major auto companies, such as Toyota, GM, Ford, and BMW, are focusing on the development of metallic BPPs. Amorphous carbon (a-C) coating are widely known to be effective at enhancing the performance of metallic BPPs. However, a-C coatings prepared by sputtering are mostly micrometers thick, which can render mass production difficult due to their low deposition rates. In this study, we investigate effects of thickness on the formation of defects and the graphitization of nanothin a-C layers deposited by magnetron sputtering from scanning electron microscope (SEM) and transmission electron microscope (TEM) observations, internal stress measurements, X-ray diffractometer (XRD) data, Raman spectra, and X-ray photoelectron spectroscopy (XPS). Furthermore, corrosion and interfacial contact resistance (ICR) test results show that an approximately 69 nm a-C layer, with a deposition time of only 15 min, can meet ex situ technical targets of US Department of Energy. As the thickness of a-C layers increases, vacancy-like defects become more pronounced, which is accompanied by stress relaxation. Furthermore, the larger the graphite-like clusters, the more sp2-hybridization carbon atoms found in loose a-C films. The good properties of nanothin a-C layers are attributed to their limited defects and proper graphitization.

Enhanced Corrosion Resistance and Interfacial Conductivity of TiC x/a-C Nanolayered Coatings via Synergy of Substrate Bias Voltage for Bipolar Plates Applications in PEMFCs.

Proton-exchange membrane fuel cells are one kind of renewable and clean energy conversion device, whose metallic bipolar plates are one of the key components. However, high interfacial contact resistance and poor corrosion resistance are still great challenges for the commercialization of metallic bipolar plates. In this study, we demonstrated a novel strategy for depositing TiC x/amorphous carbon (a-C) nanolayered coatings by synergy of 60 and 300 V bias voltage to enhance corrosion resistance and interfacial conductivity. The synergistic effects of bias voltage on the composition, microstructure, surface roughness, electrochemical corrosion behaviors, and interfacial conductivity of TiC x/a-C coatings were explored. The results revealed that the columnar structures in the inner layer were suppressed and the surface became rougher with the 300 V a-C layer outside. The composition analysis indicated that the sp2 content increased with an increase of 300 V sputtering time. Due to the synergy strategy of bias voltage, lower corrosion current densities were achieved both in potentiostatic polarization (1.6 V vs standard hydrogen electrode) and potentiodynamic polarization. With the increase of 300 V sputtering time, the interfacial conductivity was improved. The enhanced corrosion resistance and interfacial conductivity of the TiC x/a-C coatings would provide new opportunities for commercial bipolar plates.