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.     

Corrosion behavior of polyphenylene sulfide–carbon black–graphite composites for bipolar plates of polymer electrolyte membrane fuel cells

The aim of this work was to study the corrosion behavior of polyphenylene sulfide (PPS) – carbon black – graphite composites regarding their application as bipolar plates of polymer electrolyte membrane (PEM) fuel cells. Electrochemical impedance spectroscopy (EIS), potentiostatic and potentiodynamic polarization tests were used to characterize the electrochemical response of the composites in a simulated PEM fuel cell environment. Cross-sectional views of fractured specimens were observed by scanning electron microscopy (SEM). The results showed that the corrosion behavior depends on the carbon black content incorporated into the composite formulation. There was a trend of decreasing the corrosion resistance for higher carbon black contents. This behavior could be explained based on the porosity and electrical conductivity of the composites.     

Perfluorosulfonic acid ionomer – silica composite membranes prepared using hyperbranched polyethoxysiloxane for polymer electrolyte membrane fuel cells

We report on the preparation and characterization of perfluorosulfonic acid ionomer (PFSA) – silica composite membranes using hyperbranched polyethoxysiloxane (PEOS) as silica precursor. The membranes were formed via an in situ sol–gel process of PEOS in a PFSA solution and subsequent solution casting. Transmission electron microscopy and small-angle X-ray scattering data showed that at low silica content ultra-small silica particles with a size smaller than the diameter of the ionic channels were homogeneously dispersed in the PFSA matrix. Such morphology leads to enhanced proton mobility as probed by impedance spectroscopy and ¹H solid-state NMR, and eventually resulted in the improvement of fuel cell performance.     

Carbon monoxide poisoning and mitigation strategies for polymer electrolyte membrane fuel cells – A review

Polymer electrolyte membrane fuel cells (PEMFC) have received much attention due to their high power density, good start-stop capabilities and high gravimetric and volumetric power density compared with other fuel cells. However, certain technological challenges persist, which include the fact that conventional anode electrocatalysts are poisoned by low levels (few ppm) of carbon monoxide (CO). This review considers the mechanism of CO poisoning and the effects that it has on the PEMFC performance. The key parameters affecting CO poisoning are identified and methods used to mitigate the effects are discussed. These mitigation strategies are divided into three groups according to the means by which the technologies are applied: pre-treatment of reformate, on board removal of CO and in operando mitigation strategies.     

Evaluation of vacuum heat-treated α-C films for surface protection of metal bipolar plates used in polymer electrolyte membrane fuel cells

Proton exchange membrane fuel cells (PEMFCs) assembled with metal bipolar plates (BPPs) is a promising power source for new energy vehicles. However, metal BPPs have serious corrosion issues and the surface electrical performance degrades in the harsh PEMFC environment. Amorphous carbon (α-C) films exhibit improved properties with both high corrosion resistance and electrical conductivity. Subsequent vacuum heat treatment of the as-coated α-C films can change their phase composition and film structure, modifying their performance. This study prepared α-C films with a titanium interlayer on a SS316L substrate by DC balance magnetron sputtering and then subjected them to vacuum heat treatment at different temperatures (400–700 °C). These treated α-C films are systemically analyzed in terms of surface and cross-sectional morphologies, sp bond hybridization, interfacial electrical conductivity, and corrosion resistance. The results indicate that the conversion of sp³ to sp² and the compact density of α-C films are greatly enhanced with an increase in temperature, greatly improving the corrosion resistance and surface conductivity of the films. These promising results lead to a potential direction for the post-coating treatment of α-C films on metal BPPs in PEMFCs.     

Ag–polytetrafluoroethylene composite coating on stainless steel as bipolar plate of proton exchange membrane fuel cell

Forming a coating on metals by surface treatment is a good way to get high performance bipolar plate of proton exchange membrane fuel cell (PEMFC). In our research, Ag–polytetrafluoroethylene (PTFE) composite film was electrodeposited with silver-gilt solution of nicotinic acid by a bi-pulse electroplating power supply on 316 L stainless steel bipolar plate of PEMFC. Surface topography, contact angle, interfacial conductivity and corrosion resistance of the bipolar plate samples were investigated. Results showed that the defects on the Ag–PTFE composite coating are greatly reduced compared with those on the pure Ag coating fabricated under the same condition; and the contact angle of the Ag–PTFE composite coating with water is 114°, which is much bigger than that of the pure Ag coating (73°). In addition, the interfacial contact resistance of the composite coating stays as low as the pure Ag coating; and the bipolar plate sample with composite coating shows a close corrosion resistance to the pure Ag coating sample in potentiodynamic and potentiostatic tests. Coated 316 L stainless steel plate with Ag–PTFE composite coating exhibits well hydrophobic characteristic, less defects, high interfacial conductivity and good corrosion resistance, which shows a great potential of the application in PEMFC.     

Electrophoretic deposition of carbon-supported octahedral Pt–Ni alloy nanoparticle catalysts for cathode in polymer electrolyte membrane fuel cells

The advanced electrochemical catalytic activity for oxygen reduction reaction (ORR) based on the octahedral Pt–Ni alloyed catalyst has been demonstrated. However, a means of fabricating catalyst electrodes for use in PEMFCs that is cost-effective, scalable, and maintains the high activity of Pt–Ni_alloy/C has remained out of reach. Electrophoretic deposition (EPD) is a colloidal production process that has a history of successful deployment at the industrial scale. Here, we report on the facile preparation of an effective and active cathode consisting of Pt–Ni alloy loaded on the carbon cloth substrate using the electrophoretic deposition (EPD) technique, in which the optimum applied voltages and suspension pH are systematically investigated to obtain the highly porous Pt–Ni_alloy/C catalyst electrode. In a half cell test, the EPD-made Pt–Ni_alloy/C catalyst electrodes fabricated at 45 V and in a solution with a pH of 9.0 yields the best performances. On the other, as an active cathode, the EPD-made Pt–Ni_alloy/C electrodes deliver a superior performance in single cell test, with the maximum power density reaches 7.16 W/mg_Pt, ～28.1% higher than that of the spray-made Pt/C conventional electrode. The outperformance is attributed to the significantly higher porosity and surface roughness of the EPD-made electrode.     

ZrO2–SiO2/Nafion composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity

Recast Nafion^® composite membranes containing ZrO₂–SiO₂ binary oxides with different Zr/Si ratios are investigated for polymer electrolyte membrane fuel cells (PEMFCs) at temperatures above 100 °C. Fine particles of the ZrO₂–SiO₂ binary oxides, same as an inorganic filter, are synthesized from a sodium silicate and a carbonate complex of zirconium by a sol–gel technique. The composite membranes are prepared by blending a 10% (w/w) Nafion^®-water dispersion with the inorganic compound. All composite membranes show higher water uptake than unmodified membranes, and the proton conductivity increases with increasing zirconia content at 80 °C. By contrast, the proton conductivity decreases with zirconia content for the composite membranes containing binary oxides at 120 °C. The composite membranes are tested in a 9-cm² commercial single cell at both 80 °C and 120 °C in humidified H₂/air under different relative humidity (RH) conditions. Composite membrane containing the ZrO₂–SiO₂ binary oxide (Zr/Si = 0.5) give the best performance of 610 mW cm⁻¹ under conditions of 0.6 V, 120 °C, 50% RH and 2 atm.     

Evaluation of the stability and durability of Pt and Pt–Co/C catalysts for polymer electrolyte membrane fuel cells

Carbon supported Pt and Pt–Co nanoparticles were prepared by reduction of the metal precursors with NaBH₄. The activity for the oxygen reduction reaction (ORR) of the as-prepared Co-containing catalyst was higher than that of pure Pt. 30 h of constant potential operation at 0.8 V, repetitive potential cycling in the range 0.5–1.0 V and thermal treatments were carried out to evaluate their electrochemical stability. Loss of non-alloyed and, to a less extent, alloyed cobalt was observed after the durability tests with the Pt–Co/C catalyst. The loss in ORR activity following durability tests was higher in Pt–Co/C than in Pt/C, i.e. pure Pt showed higher electrochemical stability than the binary catalyst. The lower stability of the Pt–Co catalyst during repetitive potential cycling was not ascribed to Co loss, but to the dissolution–re-deposition of Pt, forming a surface layer of non-alloyed pure Pt. The lower activity of the Pt–Co catalyst than Pt following the thermal treatment, instead, was due to the presence of non-alloyed Co and its oxides on the catalyst surface, hindering the molecular oxygen to reach the Pt sites.     

Effective transport properties for polymer electrolyte membrane fuel cells – With a focus on the gas diffusion layer

Multi-phase transport of reactant and product species, momentum, heat (energy), electron and proton in the components of polymer electrolyte membrane (PEM) fuel cells forms the three inter-related circuits for mass, heat (energy) and electricity. These intertwined transport phenomena govern the operation and design, hence the performance, of such cells. The transport processes in the cell are usually determined with their respective effective transport properties due to the porous nature of PEM fuel cell components. These properties include the effective diffusion coefficient for the mass transfer, effective thermal conductivity for heat transfer, effective electronic conductivity for electron transfer, effective protonic conductivity for proton transfer, intrinsic and relative permeability for fluid flow, capillary pressure for liquid water transfer, etc. Accurate determination of these effective transport properties is essential for the operation and design of PEM fuel cells, especially at high current density operation. Thus, it is the focus of intensive research in the recent years. In this article, a review is provided for the determination of these effective transport properties through the various PEM fuel cell components, including the gas diffusion layer, microporous layer, catalyst layer and the electrolyte membrane layer. Given the simplicity of the GDL in structure compared to the other components of the cell, much more work in literature is focused on its transport properties. Hence, its review in this paper is more extensive. Various methods used for the determination of the effective transport properties with and without the presence of liquid water are reviewed, including experimental measurements, numerical modeling and theoretical analyses. Correlations are summarized for these transport properties, where available and further work in this area is provided as a direction for future work.     

Numerical investigation of tridirectionally synergetic Nafion® ionomer gradient cathode catalyst layer for polymer electrolyte membrane fuel cells

Pervious studies have compressively examined a single direction ionomer gradient cathode catalyst layer (CCL) for enhancement of polymer electrolyte membrane (PEM) fuel cells. However, a tridirectionally synergetic (TS) ionomer gradient CCL has not been investigated to date. It is reported that the design of multi-directional ionomer gradient CCL is significant for fuel cells. Therefore, this study proposes a novel TS gradient CCL for fuel cells. By implementing a three-dimensional multiphase fuel cell model, the novel TS gradient CCL is evaluated regarding internal physicochemical quantity distributions and overall cell performance. Numerical results indicate that in comparison with CCL with uniform and a single direction through-plane (TP) or in-plane (IP) ionomer gradient CCL with an identical ionomer content, the novel TS gradient CCL can enhance oxygen diffusion and proton conductivity within porous electrodes, thus improving the maximum power density by approximately 6.8%. Moreover, the optimal TS ionomer gradient CCL contributes to a reduction in coefficient variation of current density within CCL by 10.3% and 17.1% compared to that of uniform and TP(X) gradient CCLs, leading to more homogeneous internal physical quantity profiles, ultimately benefiting the stable operation and durability of fuel cells. The findings here can provide a new insight for guiding the design of ionomer gradient CCL.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

Novel doped barium cerate–carbonate composite electrolyte material for low temperature solid oxide fuel cells

A composite of a perovskite oxide proton conductor (BaCe_0.7Zr_0.1Y_0.2O_3−δ, BCZ10Y20) and alkali carbonates (2Li₂CO₃:1Na₂CO₃, LNC) is investigated with respect to its morphology, conductivity and fuel cell performance. The morphology shows that the presence of carbonate phase improves the densification of oxide matrix. The conductivity is measured by AC impedance in air, nitrogen, wet nitrogen, hydrogen, and wet hydrogen, respectively. A sharp increase of the conductivity at certain temperature is seen, which relates to the superionic phase transition at the interface phases between oxide and carbonates. Single cell with the composite electrolyte is fabricated by dry-pressing technique, using nickel oxide as anode and lithiated nickel oxide as cathode, respectively. The cell shows a maximum power density of 957 mW cm⁻² at 600 °C with hydrogen as the fuel and oxygen as the oxidant. The remarkable proton conductivity and excellent cell performance make this kind of composite material a good candidate electrolyte for low temperature solid oxide fuel cells (SOFCs).     

Insight towards kinetics and stability of carbon supported Pd–Y2O3 as cathode catalyst for polymer electrolyte fuel cells

Pd–Y₂O₃ on carbon (Pd–Y₂O₃/C) in different mass ratios of Pd to Y₂O₃ (1:1, 2:1, 3:1) were prepared and subjected as cathode electrocatalyst for polymer electrolyte fuel cells (PEFC). X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to determine the structure, crystalline size and dispersion of Pd–Y₂O₃/C respectively. The electrochemical characterizations of the electrocatalysts were evaluated from Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV). These electrocatalysts were evaluated for their catalytic activity towards oxygen reduction reaction (ORR) in fuel cell. Pd₂–Y₂O₃/C catalyst shows higher power density of 325 mW cm^?2 than Pd₁–Y₂O₃/C, Pd₃–Y₂O₃/C and Pd/C.     

Alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte for Zn–air battery

An alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte with high ionic conductivity (10⁻² S cm⁻¹) at room temperature has been prepared and applied to solid-state primary Zn–air batteries. The electrolyte shows excellent mechanical strength. The electrochemical characteristics of the batteries were experimentally investigated by means of ac impedance spectroscopy and galvanostatic discharge. The results indicate that the PEO–PVA–glass-fibre-mat composite polymer electrolyte is a promising candidate for application in alkaline primary Zn–air batteries.     

Intermediate temperature fuel cells based on doped ceria–LiCl–SrCl2 composite electrolyte

A new type of oxide-salt composite electrolyte, gadolinium-doped ceria (GDC)–LiCl–SrCl₂, was developed and demonstrated its promising use for intermediate temperature (400–700 °C) fuel cells (ITFCs). The dc electrical conductivity of this composite electrolyte (0.09–0.13 S cm⁻¹ at 500–650 °C) was 3–10 times higher than that of the pure GDC electrolyte, indicating remarkable proton or oxygen ion conduction existing in the LiCl–SrCl₂ chloride salts or at the interface between GDC and the chloride salts. Using this composite electrolyte, peak power densities of 260 and 510 mW cm⁻², with current densities of 650 and 1250 mA cm⁻² were achieved at 550 and 625 °C, respectively. This makes the new material a good candidate electrolyte for future low-cost ITFCs.     

Effects of Pt loading in the anode on the durability of a membrane–electrode assembly for polymer electrolyte membrane fuel cells during startup/shutdown cycling

A polymer electrolyte membrane fuel cell (PEMFC) stack of a fuel cell vehicle (FCV) is inevitably exposed to reverse current conditions, which are formed by the oxygen reduction reaction (ORR) induced at the anode with a hydrogen/air boundary during startup/shutdown processes. With an increase in the reverse current, the degradation rate of the cathode that experiences a highly corrosive condition (locally high potential) increases. In this work, the anode Pt loading is decreased from 0.4 to 0.1 mg cm⁻² to decrease the reverse current. The decrease in the anode Pt loading is found to decrease the hydrogen oxidation rates (HOR) during normal operation, but this loading decrease barely affected the cell performance. However, a decrease in the anode Pt loading can significantly decrease the reverse current, leading to a diminished cathode degradation rate during startup/shutdown cycling. It is revealed by slow decreases in the cell performance (i–V curves) and electrochemical active surface area (EAS), and a slow increase in the charge-transfer resistance (R_ct), which can be attributed to corrosion of the carbon support and dissolution/migration/agglomeration of the platinum catalyst.     

Development of trimetallic Ni–Cu–Zn anode for low temperature solid oxide fuel cells with composite electrolyte

Trimetallic alloys of Ni_0.6Cu_0.4−xZn_x (x = 0, 0.1, 0.2, 0.3, 0.4) have been investigated as promising anode materials for low temperature solid oxide fuel cells (SOFCs) with composite electrolyte. The alloys have been obtained by reduction of Ni_0.6Cu_0.4−xZn_xO oxides, which are synthesized by using the glycine–nitrate process. Increasing the Zn content x decreases the particle sizes of the oxides at a given sintering temperature. Fuel cells have been constructed using lithiated NiO as cathode and as-prepared alloys as anodes based on the composite electrolyte. Peak power densities are observed to increase with the increasing Zn addition concentration into the anode. The maximum power density of 624 mW cm⁻² at 600 °C, 375 mW cm⁻² at 500 °C has been achieved for the fuel cell equipped with Ni_0.6Zn_0.4 anode. A.c. impedance results show that the resistances dramatically decrease with increasing temperatures under open circuit voltage state. Both cathodic and anodic interfacial polarization resistances increase with the amplitude of applied DC voltage. Possible reaction process for H₂ oxidation reaction at anode based on composite electrolyte has been proposed for the first time. The stability of the fuel cell with Ni_0.6Cu_0.2Zn_0.2 composite anode has been investigated. The results indicate that the trimetallic Ni_0.6Cu_0.4−xZn_x anodes are considerable for low temperature SOFCs.     

Voltage–time behavior of a polymer electrolyte membrane fuel cell stack at constant current discharge

Empirical equations were developed to describe the voltage–time behavior of polymer electrolyte membrane fuel cell (PEMFC) stacks at constant current discharge. When either ambient temperature or discharge current is too high, the experimental voltage–time curves exhibit rapidly falling cell voltage within a short discharge time. Various experimental voltage–time curves have been fitted very well with empirical equations at different discharge currents and ambient temperatures. The effect of parameters of the empirical equations on the shape of voltage–time curve is also analyzed. Inadequate mass-transfer is likely a reason for the voltage falling down rapidly, and polymer electrolyte membrane dehydration is responsible for the inclination of the voltage–time curves. The empirical equations are helpful for forecasting and explaining the long-term discharge performance of the PEMFC stacks.