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.     

Evaluation of silver-coated stainless steel bipolar plates for fuel cell applications

In this study, computer-aided design and manufacturing (CAD/CAM) technology were applied to develop and produce stainless steel bipolar plates for DMFC (direct methanol fuel cell). Effect of surface modification on the cell performance of DMFC was investigated. Surface modifications of the stainless steel bipolar plates were made by the electroless plating method. A DMFC consisting of silver coated stainless steel as anode and uncoated stainless steel as cathode was assembled and evaluated. The methanol crossover rate (R_c) of the proton exchange membrane (PEM) was decreased by about 52.8%, the efficiency (E_f) of DMFC increased about 7.1% and amounts of methanol electro-oxidation at the cathode side (M_co) were decreased by about 28.6%, as compared to uncoated anode polar plates. These measurements were determined by the transient current and mathematical analysis.     

Evaluation of a compression molded composite bipolar plate for direct methanol fuel cell

A polymer–graphite composite bipolar plate of direct methanol fuel cell (DMFC) was fabricated by a compression molding method. The electrical conductivity and electrochemical behavior of the composite material under DMFC operating conditions were evaluated. The results show that the composite bipolar plate has a good electrical conductivity. Moreover, the through-plane conductivity of the composite material is higher than the in-plane one, which is ascribed to the anisotropic property of the composite bipolar plate resulted from the compression molding process. Corrosion tests show that the stable current density is below 10 μA cm⁻² under both anode and cathode conditions of DMFC. The discharge test of the DMFC single cell also presents a satisfactory result.     

Investigation of bipolar plate geometry on direct methanol fuel cell performance

The effect of bipolar plate (BPP) channel width on the performance of a single-cell direct methanol fuel cell (DMFC) stack was investigated. Three BPPs with a single-channel serpentine configuration were fabricated with three different channel widths having the same effective flow areas. Experimental tests showed that the fuel cell with the narrowest channel width had the best overall performance while the one with the widest channel width had the worst overall performance. A computational fluid dynamics (CFD) model was developed and simulated to investigate and understand the reasons for this change in performance. The CFD simulation showed that in the narrower channel the diffusion of the fuel within the diffusion layer was higher and the fuel distribution was more uniform. However, the pressure drop across the inlet and outlet was higher in the narrower channel, which increased the pumping power requirements.     

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.     

Performance and long-term stability of Ti metal and stainless steels as a metal bipolar plate for a direct methanol fuel cell

In this study, STS 316L (Stainless Steel 316L), STS 430, and Ti metal are investigated as metal bipolar plates for a direct methanol fuel cell (DMFC). The corrosion resistance of these materials is investigated by potentiodynamic and chronoamperometry tests. Their cell performance and long-term stability are then studied under a real fuel cell test. The corrosion resistance of the metal bipolar plates is in the order of Ti > STS 316L > STS 430. However, the results of the real fuel cell test differ from the results of the corrosion resistance. Ti shows the lowest performance due to a sharp performance decrease in ohmic loss regions, while STS 430 shows a lower performance decrease in ohmic loss regions. Although STS 430 has less resistance to corrosion than STS 316L in the simulated environment, STS 430 performs better as a metal bipolar plate for a DMFC than STS 316L, particularly, with regard to cell performance, cell resistance, and durability.     

Simplified model for the direct methanol fuel cell anode

A kinetic model for the anode of the direct methanol fuel cell (DMFC) is presented. The model is based on the generally accepted dual site mechanism of methanol oxidation, in aqueous solution, on well characterized Pt–Ru catalyst and it can predict the performance of the electrode as a function of cell temperature, anode potential and methanol concentration. In addition the model also generates data regarding the surface coverage of significant adsorbates involved in methanol oxidation on the dual site catalyst.     

Plasma-nitrided austenitic stainless steel 316L as bipolar plate for PEMFC

Stainless steel bipolar plates for the polymer electrolyte membrane (PEM) fuel cell offer many advantages over conventional machined graphite. Austenitic stainless steel 316L is a traditional candidate for metal bipolar plates. However, the interfacial ohmic loss across the metallic bipolar plate and membrane electrode assembly due to corrosion increases the overall power output of PEMFC. Plasma nitriding was applied to improve the surface performance of 316L bipolar plates. A dense _γN${\gamma }_{\mathrm{N}}$ phase layer was formed on the surface. Polarization curves in the solution simulating PEMFC environment and interfacial contact resistance were measured. The results show that the corrosion resistance is improved and the interfacial contact resistance (ICR) is decreased after plasma nitriding. In comparison with the untreated 316L, the ICR between the carbon paper and passive film for the plasma-nitrided 316L decreases at the same condition and lowers with increasing pH value.     

Development of an advanced MEA to use high-concentration methanol fuel in a direct methanol fuel cell system

Despite serious methanol crossover issues in Direct Methanol Fuel Cells (DMFCs), the use of high-concentration methanol fuel is highly demanded to improve the energy density of passive fuel DMFC systems for portable applications. In this paper, the effects of a hydrophobic anode micro-porous layer (MPL) and cathode air humidification are experimentally studied as a function of the methanol-feed concentration. It is found in polarization tests that the anode MPL dramatically influences cell performance, positively under high-concentration methanol-feed but negatively under low-concentration methanol-feed, which indicates that methanol transport in the anode is considerably altered by the presence of the anode MPL. In addition, the experimental data show that cathode air humidification has a beneficial effect on cell performance due to the enhanced backflow of water from the cathode to the anode and the subsequent dilution of the methanol concentration in the anode catalyst layer. Using an advanced membrane electrode assembly (MEA) with the anode MPL and cathode air humidification, we report that the maximum power density of 78 mW/cm² is achieved at a methanol-feed concentration of 8 M and cell operating temperature of 60 °C. This paper illustrates that the anode MPL and cathode air humidification are key factors to successfully operate a DMFC with high-concentration methanol fuel.     

Zeolite beta-filled chitosan membrane with low methanol permeability for direct methanol fuel cell

Zeolite beta particles with different sizes and narrow size distribution were hydrothermally synthesized and incorporated into chitosan (CS) matrix to prepare CS/zeolite beta hybrid membranes for direct methanol fuel cell (DMFC). It was found that the chitosan membrane filled by zeolite beta particles about 800 nm in size exhibited the lowest methanol permeability, which can be ascribed to their optimum free volume and methanol diffusion characteristics. To further improve the performances of CS/zeolite beta hybrid membranes, zeolite beta particles about 800 nm in size were sulfonated via three different approaches. The results indicated that the introduction of sulfonic groups could reduce the methanol permeability further as a result of the enhanced interfacial interaction between zeolite beta and chitosan matrix. Furthermore, in terms of the overall selectivity index, CS/zeolite beta hybrid membranes were comparable to Nafion^® 117 membrane at low methanol concentration (2 mol L⁻¹) and much better at high methanol concentration (12 mol L⁻¹).     

Pt-Ru electrocatalysts supported on ordered mesoporous carbon for direct methanol fuel cell

Pt-Ru electrocatalysts supported on ordered mesoporous carbon (CMK-3) were prepared by the formic acid method. Catalysts were characterized applying energy dispersive X-ray analyses (EDX) and X-ray diffraction (XRD). Methanol and carbon monoxide oxidation was studied electrochemically by cyclic voltammetry, and current-time curves were recorded in a methanol solution in order to establish the activity towards this reaction under potentiostatic conditions. The physicochemical and electrochemical properties of the Pt-Ru catalysts supported on CMK-3 carbon were compared with those of electrocatalysts supported on Vulcan XC-72 and commercial catalyst from E-TEK. Additionally, in order to complete this study, Pt electrocatalysts supported on CMK-3 and Vulcan XC-72 were prepared by the same method and were used as reference. Results showed that the Pt-Ru/CMK-3 catalyst presented the best electrocatalytic activity towards the CO oxidation and, therefore, good perspectives to its application in DMFC anodes. On the other hand, the activity of the Pt-Ru/CMK-3 catalyst towards methanol oxidation was higher than that of the commercial Pt-Ru/C (E-TEK) catalyst on all examined potentials, confirming the potential of the bimetallic catalysts supported on mesoporous carbons.     

Palladium selenides as active methanol tolerant cathode materials for direct methanol fuel cell

Palladium selenides, PdSe, Pd₃Se and PdSe₂ have been prepared by the hydrothermal method and investigated for their structural and electrocatalytic properties toward the oxygen reduction reaction (ORR) using SEM/TEM, XRD, cyclic and linear sweep voltammetries. The crystallites of PdSe and PdSe₂ are found to follow tetragonal and orthorhombic crystal structures, respectively. The PdSe electrode in 0.5 M H₂SO₄ exhibits significantly higher electrocatalytic activity than the Pd₃Se or PdSe₂ electrode under similar experimental conditions. Further, a change in the palladium/selenium ratio from unity in the catalyst results in low ORR activity.     

A robust methanol concentration sensing technique in direct methanol fuel cells and stacks using cell dynamics

The electrochemical behaviour of direct methanol fuel cells (DMFCs) is sensitive to methanol concentration; thus, to avoid external sensors, it is a promising candidate to monitor the concentration of methanol in the fuel circulation loop, which is central to the efficient operation of direct methanol fuel cell systems. We address this issue and report on an extremely robust electrochemical methanol sensing technique that is not sensitive to temperature, cell degradation and membrane electrode assembly (MEA) type. We develop a temperature independent empirical correlation of the dynamic response of cell voltage to step changes in current with methanol concentration. This equation is successfully validated under various operating scenarios at both the single cell and stack levels. Our sensing method achieves an impressive accuracy of ±0.1 M and this is expected to increase the reliability of methanol sensing and simplify the control logic of DMFC systems.     

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.     

Systematic approach for modeling methanol mass transport on the anode side of direct methanol fuel cells

A systematic method for modeling direct methanol fuel cells, with a focus on the anode side of the system, is advanced for the purpose of quantifying the methanol crossover phenomenon and predicting the concentration of methanol in the anode catalyst layer of a direct methanol fuel cell. The model accounts for fundamental mass transfer phenomena at steady state, including convective transport in the anode flow channel, as well as diffusion and electro-osmotic drag transport across the polymer electrolyte membrane. Experimental measurements of methanol crossover current density are used to identify five modeling parameters according to a systematic parameter estimation methodology. A validation study shows that the model matches the experimental data well, and the usefulness of the model is illustrated through the analysis of effects such as the choice fuel flow rate in the anode flow channel and the presence of carbon-dioxide bubbles.     

Effect of variation of hydrophobicity of anode diffusion media along the through-plane direction in direct methanol fuel cells

Reducing methanol crossover from the anode to cathode in direct methanol fuel cells (DMFCs) is critical for attaining high cell performance and fuel utilization, particularly when highly concentrated methanol fuel is fed into DMFCs. In this study, we present a novel design of anode diffusion media (DM) wherein spatial variation of hydrophobicity along the through-plane direction is realized by special polytetrafluoroethylene (PTFE) coating procedure. According to the capillary transport theory for porous media, the anode DM design can significantly affect both methanol and water transport processes in DMFCs. To examine its influence, three different membrane-electrode assemblies are fabricated and tested for various methanol feed concentrations. Polarization curves show that cell performance at high methanol feed concentration conditions is greatly improved with the anode DM design with increasing hydrophobicity toward the anode catalyst layer. In addition, we investigate the influence of the wettability of the anode microporous layer (MPL) on cell performance and show that for DMFC operation at high methanol feed concentration, the hydrophilic anode MPL fabricated with an ionomer binder is more beneficial than conventional hydrophobic MPLs fabricated with PTFE. This paper highlights that controlling wetting characteristics of the anode DM and MPL is of paramount importance for mitigating methanol crossover in DMFCs.     

Sensor-less control of methanol concentration based on estimation of methanol consumption rates for direct methanol fuel cell systems

Adequate control over the concentration of methanol is critically needed in operating direct methanol fuel cell (DMFC) systems, because performance and energy efficiency of the systems are primarily dependent on the concentration of methanol feed. For this purpose, we have built a sensor-less control logic that can operate based on the estimation of the rates of methanol consumption in a DMFC. The rates of methanol consumption are measured in a cell and the resulting data are fed as an input to the control program to calculate the amount of methanol required to maintain the concentration of methanol at a set value under the given operating conditions of a cell. The sensor-less control has been applied to a DMFC system employed with a large-size single cell and the concentration of methanol is found to be controlled stably to target concentrations even though there are some deviations from the target values.     

Testing of carbon supported Pd-Pt electrocatalysts for methanol electrooxidation in direct methanol fuel cells

In the present work, a detailed characterization of the electrochemical behavior of carbon supported Pd-Pt electrocatalysts toward CO and methanol electrooxidation in direct methanol fuel cells is reported. Technical electrodes containing an ionomer in their catalyst layer were prepared for this purpose. CO and methanol electrooxidation reactions were used as test reactions to compare the electrocatalytic behavior of bimetallic supported nanoparticles in acidic liquid electrolyte and in solid polymer electrolyte (real fuel cell operating conditions). Experimental results in both environments are consistent and show that the electrochemical behavior of carbon supported Pd-Pt depends on their composition, giving the best performance in direct methanol single fuel cell with a Pd:Pt atomic ratio of 25:75 in the catalyst.     

Polybenzimidazole/zwitterion-coated polyamidoamine dendrimer composite membranes for direct methanol fuel cell applications

The zwitterion-coated polyamidoamine (ZC-PAMAM) dendrimer with ammonium and sulfonic acid groups has been synthesized and used as filler for the preparation of PBI-based composite membranes for direct methanol fuel cells. Polybenzimidazole (PBI)/ZC-PAMAM dendrimer composite membranes were prepared by casting a solution of PBI and ZC-PAMAM dendrimer, and then evaporating the solvent. The presence of ZC-PAMAM dendrimer was confirmed by FT-IR and energy-dispersive X-ray spectroscopy (EDS) mapping of sulfur and oxygen elements. The water uptake, swelling degree, proton conductivity, and methanol permeability of the membranes increased with the ZC-PAMAM dendrimer content. For the PBI/ZC-PAMAM-20 membrane with 20 wt% of ZC-PAMAM, it shows a proton conductivity of 1.83 × 10⁻² S/cm at 80 °C and a methanol permeability of 5.23 × 10⁻⁸ cm² s⁻¹. Consequently, the PBI/ZC-PAMAM-20 demonstrates a maximum power density of 26.64 mW cm⁻² in a single cell test, which was about 2-fold higher than Nafion-117 membrane under the same conditions.     

A self-pumping and self-breathing micro direct methanol fuel cell with polymer bipolar plates

A passive micro direct methanol fuel cell (DMFC) for reducing volume and parasitic power is designed and fabricated using several integrated technologies. New bipolar plates with tapered channels at the anode and a pillar array at the cathode are first applied to a passive micro-DMFC. The substrate of the bipolar plates made of acrylonitrile butadiene styrene (ABS) is hot embossed with two molds, fabricated by UV-LIGA and micro machining. To make the bipolar plates conductive and hydrophilic, a nickel layer is electroplated on the ABS plates, and three PDDA/PSS bi-layers are self-assembled onto the nickel layer. The bipolar plates are produced using hot embossing, a low cost, highly accurate batch process. A single cell is assembled to verify the self-pumping function, and it can generate a peak power density of 7.4 mW cm⁻² with a 3 M methanol solution. The fuel cell is verified to work in three different orientations. When the fuel cell is placed horizontally, the self-pumping rate is about 0.1-0.15 mL h⁻¹. And the fuel cell can work through self-pumping for 5 h under this condition.