Development of nano-catalyzed membrane for PEM fuel cell applications

Nano-catalyzed membrane with different platinum (Pt) catalyst loadings (0.25 to 1 mg cm^?2) was investigated for proton exchange membrane fuel cell applications, and the Pt loading on the Nafion membrane was prepared by non-equilibrium impregnation reduction method. The prepared catalyzed membranes were subjected to various characterisations, namely, X-ray diffraction, high-resolution scanning electron microscopy (HRSEM) with energy-dispersive X-ray, cyclic voltammetry, polarisation and electrochemical impedance spectroscopy. The polycrystalline fcc cubic structure and the particle size of Pt catalyst were estimated by X-ray diffraction analysis. The membrane with 0.4 mg cm^?2 of Pt loading exhibits a favourable surface morphology which is confirmed by HRSEM image. Electrochemical investigations were clearly evident that the uniform distributions of Pt particles with fine pores on Nafion membrane facilitated the three-phase boundary which leads to a better cell performance. Electrochemical impedance spectroscopy demonstrated that the cell constructed using 0.4 mg cm^?2 of platinum-loaded membrane has lower resistance than the other Pt loading.     

Improvement in performance of a direct ethanol fuel cell: Effect of sulfuric acid and Ni-mesh

A direct ethanol fuel cell (DEFC) is developed with low catalyst loading at anode and cathode compared to that reported in the literature. Pt/Ru (40%:20% by wt.)/C and Pt-black were used as anode and cathode catalyst with loadings in the range of 0.5–1.2 mg/cm². The temperatures of anode and cathode were varied from 34 °C to 110 °C, and the pressure was maintained at 1 bar. Although low catalyst loading was used, the cell performance is enhanced by 40–50% with the use of low concentration of sulfuric acid in ethanol and Ni-mesh as current collector at the anode. The power density 15 mW/cm² at 32 mA/cm² of current density is obtained from the single cell with 0.5 mg/cm² loading of Pt–Ru/C at anode (90 °C) and Pt-black at cathode (110 °C). The performance of DEFC increases with the increase in ethanol and sulfuric acid concentrations, electrocatalyst loadings up to 1 mg cm⁻² at anode and cathode. However, the performance of DEFC decreases with further increase in electrocatalyst loading.     

Energy material - the role of silicotungstic acid and fly ash in sulfonated poly (ether sulfone) composites for PEMFC applications

The composite polymer electrolyte membranes were prepared from sulfonated poly (ether sulfone) (SPES), silicotungstic acid (STA) and fly ash (FA). Post sulfonation process was adopted to synthesize SPES using sulphuric and chlorosulfonic acid. The prepared electrolyte membranes were examined by water uptake capacity, swelling ratio, ion-exchange ability, proton conductivity, thermal stability and electrochemical performance for evaluating the pertinence of these membranes in fuel cell applications. As such the pristine membrane restricts with the proton conductivity of 0.042?S cm^?1 at 30?°C and 0.060?S cm^?1 at 90?°C while the polymer composite membrane, SP-STA-FA-10 reveals the maximum conductivity of 0.054?S cm^?1 at 30?°C and 0.073?S cm^?1 at 90?°C. It also exhibits good thermal stability than that of the pure membrane. The membrane electrode assemblies (MEAs) have been successfully developed from SPES as well as SP-STA-FA-10 membranes and their electrochemical performance were studied the wide range of current density. Herein, the composite membranes derived from SPES, STA and FA can be viable candidates for fuel cell applications.     

气体扩散电极参数对阴离子交换膜燃料电池性能的影响

优化了碱性阴离子交换膜燃料电池（AAEMFC）使用的气体扩散电极（GDE）,发现催化层中PTFE含量与催化剂担载量对电池性能与其电化学动力学特征影响很大.采用i-V曲线,开路电压,电池内阻与在线的电化学阻抗谱与动力学分析,评估了所制GDE的电化学性能.在所研究的AAEMFC电极催化层中,PTFE的最佳含量是20%,Pt载量对膜电极三相界面、催化层导电性与催化剂利用率的影响极大.当制备的GDE催化层中Pt/C的Pt载量为1.0mg/cm²,PTFE含量为20%时,AAEMFC的峰电流密度在50^oC达到了213mW/cm².兼顾Pt催化剂的利用率与成本,在没有明显影响电池性能的情况下,Pt的担载量可降至0.5mg/cm².     

Calculating a Characteristic Bulk Current Density in the Cathode of a Hydrogen-Oxygen Fuel Cell with a Solid Polymer Electrolyte

The magnitude of currents of electrodes in hydrogen-oxygen fuel cells of all types is shown to be fully determined by values of the effective coefficient of gas diffusion, the effective coefficient of ionic conduction, and the characteristic bulk current density. The characteristic bulk current density is estimated in two versions for cathodes with Nafion: the catalyst is distributed in the bulk of substrate grains or at their external surface. The currents commensurate with those observed in experiments are given only by the second version. Means of computer-aided simulation are used to imitate the formation of fractal films composed of the catalyst particles on the surface substrate grains. The simulation means made it possible to link the magnitude of the specific surface area of platinum particles with its weight content in substrate grains. Electrochemical characteristics of the cathode with Nafion-the potential dependence of the optimum magnitude of the overall current and the thicknesses of the active layer and the weight of platinum in it, as well as the magnitudes of the optimum current generated by a unit weight of platinum—are calculated. A notion of “ norm” is introduced for the characteristic bulk current density of the cathode. 1 × 10^?3 A cm^?3 is the electrochemical-process intensity, which the technology of preparation of active layers of cathodes can provide at this stage in the development of fuel cells with a solid polymer electrolyte.     

Effects of humidity and temperature on the electrochemical activities of H2/O2 PEMFCs using hybrid membrane electrolytes

Electrochemical characteristics of single cell performances at various humidity conditions and constant temperatures of 40?100 °C using membrane electrode assemblies (MEAs) were studied. The MEAs consist of alternative proton-conducting hybrid membrane electrolyte and noble Pt/C catalyst for the H₂/O₂ proton exchange membrane fuel cells (PEMFCs). The function of humidity on the cell performances was investigated at larger current density values of 501 mA cm^?2 and constant cell temperatures of 80 and 90 °C and the relative humidity of 100 %. The power density value of 400 mW cm^?2 was obtained when the same MEA at similar operating conditions was used. The effects of temperature on the single cell performances were investigated at various temperature ranges of 40–100 °C and constant relative humidity of 50, 70, and 100 %. The maximum current density and power density values of about 600 mA cm^?2 and 160 mW cm^?2, respectively, were obtained at 90 °C with 100 % RH. The results were compared with the reported results of Nafion membrane and similar hybrid membranes operating at low temperatures for H₂/O₂ fuel cells. Finally, the results provided an alternative proton-conducting electrolyte as promising candidate for low/intermediate temperature operating H₂/O₂ fuel cells.     

A completely spray-coated membrane electrode assembly

We present a proton exchange membrane fuel cell (PEMFC) manufacturing route, in which a thin layer of polymer electrolyte solution is spray-coated on top of gas diffusion electrodes (GDEs) to work as a proton exchange membrane. Without the need for a pre-made membrane foil, this allows inexpensive, fast, large-scale fabrication of membrane-electrode assemblies (MEAs), with a spray-coater comprising the sole manufacturing device. In this work, a catalyst layer and a membrane layer are consecutively sprayed onto a fibrous gas diffusion layer with applied microporous layer as substrate. A fuel cell is then assembled by stacking anode and cathode half-cells with the membrane layers facing each other. The resultant fuel cell with a low catalyst loading of 0.1 mg Pt/cm² on each anode and cathode side is tested with pure H₂ and O₂ supply at 80 °C cell temperature and 92% relative humidity at atmospheric pressure. The obtained peak power density is 1.29 W/cm² at a current density of 3.25 A/cm². By comparison, a lower peak power density of 0.93 W/cm² at 2.2 A/cm² is found for a Nafion NR211 catalyst coated membrane (CCM) reference, although equally thick membrane layers (approx. 25 μm), and identical catalyst layers and gas diffusion media were used. The superior performance of the fuel cell with spray-coated membrane can be explained by a decreased low frequency (mass transport) resistance, especially at high current densities, as determined by electrochemical impedance spectroscopy.     

The Comparability of Pt to Pt‐Ru in Catalyzing the Hydrogen Oxidation Reaction for Alkaline Polymer Electrolyte Fuel Cells Operated at 80 °C

The Pt‐catalyzed hydrogen oxidation reaction (HOR) for alkaline polymer electrolyte fuel cells (APEFCs) has been one of the focus subjects in current fuel‐cell research. The Pt catalyst is inferior for HOR in alkaline solutions, and alloying with Ru is an effective promotion strategy. APEFCs with Pt‐Ru anodes have provided a performance benchmark over 1 W cm^?2 at 60 °C. The Pt anode is now found to be in fact as good as the Pt‐Ru anode for APEFCs operated at elevated conditions. At 80 °C with appropriate gas back‐pressure, the cell with a Pt anode exhibits a peak power density of about 1.9 W cm^?2, which is very close to that with a Pt‐Ru anode. Even by decreasing the anode Pt loading to 0.1 mg cm^?2, over 1.5 W cm^?2 can still be achieved at 80 °C. This finding alters the previous understanding about the Pt catalyzed HOR in alkaline media and casts a new light on the development of practical and high‐power APFEC technology.     

Performance Assessment of a Perfluorosulfonic Acid‐type Membrane (i. e. Nafion™ 115) for an Enzymatic Fuel Cell

A high power enzymatic fuel‐cell was anticipated by using a recently developed glucose oxidase (GOx) immobilized bio‐anode, a conventional platinum?carbon based cathode and a popular high performance 125 μ‐thick perfluorosulfonic acid‐type proton exchange membrane (i. e. Nafion® 115). Unexpected current density decay from 2.13 mA cm^?2 to 0.28 mA cm^?2 was observed within 2 hours. Polarization measurements and AC impedance analysis indicated that loss of performance was linked to the membrane behavior. Ion exchange between buffer solution and membrane was perceived as the main cause for the fast performance loss. Saturation of the membrane with the cation in the buffer solution diminished proton transfer needed for cathode reaction. Charge transfer resistances, obtained from AC impedance data, increased with time substantially due to cation exchange within membrane. Replacement of membrane with the same enzyme electrode and cathode has resulted 100 % current density recovery on the fuel cell performance. It was concluded that a membrane, not affected by the buffer cations, was required for successful enzymatic fuel cell applications.     

Enhanced stability of symmetrical polymer electrolyte membrane fuel cell single cells based on novel hierarchical microporous-mesoporous carbon supports

Fuel cell electrodes were prepared from Pt nanocluster activated hierarchical microporous-mesoporous carbon powders. The carbon supports were synthesized from molybdenum carbide applying the high-temperature chlorination method. Six different synthesis temperatures within the range from 600 to 1000 °C were used for preparation of carbon supports. Thermogravimetric analysis, X-ray diffraction, low-temperature nitrogen sorption, and high-resolution scanning electron microscopy methods were used to characterize the structure of the electrode materials and symmetrical membrane electrode assemblies (MEAs). The MEAs prepared were used to conduct the proton exchange membrane fuel cell (PEMFC)single-cell measurements. The polarization and power density curves for single cells were calculated to evaluate the activity of the catalyst materials synthesized. The electrochemically active surface area (from 2.4 to 11.9 m² g^?1) was obtained in order to estimate the contact surface areas of platinum and Nafion® electrolyte. The values of the electrolyte resistance, polarization resistance, and cell degradation rate were calculated from electrochemical impedance spectroscopy data. The carbon materials synthesized within temperature range from 600 to 850 °C were found to be the most suitable supports for PEMFCs, having higher maximum power density values and better stability (cell potential degradation 240 μV h^?1) than commercial carbon-based (Vulcan XC72; 670 μV h^?1) single cells.     

Improved interfacial adhesion of membrane electrode assemblies using polymer binders and pore-filling membranes in alkaline membrane fuel cells

The development of alkaline membrane fuel cells (AMFCs) will enable the use of non-platinum catalysts and hydrocarbon-based electrolyte membranes. Such catalysts are intrinsically stable and have activities similar to that of platinum in an alkaline environment. A pore-filling membrane has been made from a porous, high-density polyethylene substrate to fabricate durable, AMFC membrane electrode assemblies (MEAs). Because of the low binding ability of the hydrocarbon ionomer in the preparation of AMFC MEAs, polymer binders were added to the catalyst slurries to form a firmly bound interface. A content of 20 wt% polyethylene (PE) binder, the same material as the porous substrate in the pore-filling membrane, exhibits the best attachment of the non-platinum catalyst particles to the pore-filling, hydrocarbon anion-exchange membranes. The addition of a PE binder improves adhesion at the MEA interface and diminished contact resistance. The improved durability of the MEA is confirmed by continuous, constant-voltage operation. Adhesion between the cathode catalyst layer and the pore-filling membrane is also investigated after mild hot-pressing to test the use of decal method in the fabrication of AMFCs. The catalyst layer with the PE binder was completely transferred to the pore-filling membrane at 50 °C and 30 bar?cm^?2, but not for the PTFE binder.     

Current challenges related to the deployment of shape-controlled Pt alloy oxygen reduction reaction nanocatalysts into low Pt-loaded cathode layers of proton exchange membrane fuel cells

The reduction of the amount of platinum used in proton exchange membrane fuel cell cathodes at constant power density helps lower the cell stack cost of fuel cell electric vehicles. Recent screening studies using the thin film rotating disk electrode technique have identified an ever-growing number of Pt-based nanocatalysts with oxygen reduction reaction Pt-mass activities that allow for a substantial projected decrease in the geometric platinum loading at the cathode layer. However, the step from a rotating disk electrode test to a membrane electrode assembly test has proved a formidable task. The deployment of advanced, often shape-controlled dealloyed Pt alloy nanocatalysts in actual cathode layers of proton exchange membrane fuel cells has remained extremely challenging with respect to their actual catalytic activity under hydrogen/oxygen flow, their hydrogen/air performance at high current densities, and their morphological stability under prolonged fuel cell operations. In this review, we discuss some of these challenges, yet also propose possible solutions to understand the challenges and to eventually unfold the full potential of advanced Pt-based alloy oxygen reduction reaction catalysts in fuel cell electrode layers.     

Performance of plasma sputtered fuel cell electrodes with ultra-low Pt loadings

Ultra-low Pt content PEMFC electrodes have been manufactured using magnetron co-sputtering of carbon and platinum on a commercial E-Tek^® uncatalyzed gas diffusion layer in plasma fuel cell deposition devices. Pt loadings of 0.16 and 0.01 mg cm^?2 have been realized. The Pt catalyst is dispersed as small clusters with size less than 2 nm over a depth of 500 nm. PEMFC test with symmetric electrodes loaded with 10 μg cm^?2 led to maximum reproducible power densities as high as 0.4 and 0.17 W cm^?2 with Nafion^®212 and Nafion^®115 membranes, respectively.     

Development of hydrogen–air fuel cells with membranes based on sulfonated polyheteroarylenes

Proton-conducting membranes based on sulfonated polynaphthoyleneimide (PNI) and polytriazole (PTA) are synthesized that can be used in portable hydrogen–air fuel cells (HAFC). Membrane–electrode assemblies (MEAs) based on sulfonated PNI and PTA membranes in individual HAFC manifested power and voltammetric characteristics exceeding the characteristics of MEA based on the commercial Nafion-212 membrane. Thus, the current density of 320 mA cm^–2 and the power density of 160 mW cm^–2 are obtained at the room temperature with no pressure or gas humidification at the voltage of 0.5 V. Also activity of the oxygen electroreduction Pt–Fe/C (30 wt % of metals in total) catalyst synthesized on the basis of coordination compounds is tested in MEA HAFC. It is shown that the values of power for MEAs with the cathodic Pt–Fe/C catalyst at the voltage of 0.5 V, at the room temperature, without additional pressure and gas humidification considerably exceed the corresponding values for MEAs with the commercial E-TEK 20% Pt/C catalyst.     

质子交换膜燃料电池电极的一种新的制备方法

提出一种新的电极制备方法 ,在薄层催化层电极制备中加入造孔剂 ,并使用喷涂方法 ,使质子交换膜燃料电池 (PEMFC)电极中铂担量降到 0 .0 2mgPt/cm2 .与文献方法相比 ,新方法过程简单、成本低、易放大 .并通过实验得到电极的最佳组成为 :催化剂 :造孔剂 :Nafion =3:3:1 .采用此方法制备的电极 (0 .0 2mgPt/cm2 )与Nafion 1 1 5膜组装成电池 ,单池工作电压为 0 .7V时 ,每毫克铂可产生 2 0A的电流 ,每千瓦电池组仅需 72mgPt .     

Alternative proton-conducting electrolytes and their electrochemical performances

This study was focused on the performances of membrane electrode assemblies (MEAs) consisting of the proton–conducting 90PVA/3PWA/4GPTMS/1P₂O₅/2Gl and 80PVA/10PWA/6GPTMS/2P₂O₅/2Gl hybrid membranes as electrolytes together with a Pt/C electrode for proton exchange membrane fuel cells. The MEAs were fabricated and tested as a function of temperature and humidity, and yielded a current density value of about 350?mA?cm^?2 at 60?°C and 100% relative humidity (RH) for the membrane electrolyte 80PVA/10PWA/6GPTMS/2P₂O₅/2Gl. These values were compared with Nafion? membranes, and the single-cell performances based on proton-conducting organic/inorganic hybrid electrolytes were discussed. The test conditions employed were equivalent for each MEA that had an active area of 5?cm². These hybrid membranes showed a high proton conductivity in the range of 10^?3–10^?2 S cm^?1 at low temperatures, i.e., 60, 80, and 90?°C, and 50%, 75%, and 100% RH.     

Co-extrusion of multilayer poly(m-xylylene adipimide) nanocomposite films for high oxygen barrier packaging applications

Multilayer packaging films incorporating a montmorillonite layered silicate (MLS)/poly(m-xylylene adipimide) (MXD6) nanocomposite as the oxygen barrier layer and low-density polyethylene (LDPE) as the moisture resistant layer were produced through the co-extrusion process at the laboratory and pilot scale level. Extrusion screw speeds were varied from 30 to 130 rpm in order to produce samples with varying layer thicknesses. The multilayer film structure was scaled up from the laboratory scale to the pilot-level scale based on oxygen transmission data obtained from the laboratory-scale process parameters. Laboratory-scale film results indicated that the film which demonstrated an optimal oxygen transmission rate (OTR) of 0.3 cm³/(m² day) at 60%RH and water vapor transmission rate (WvTR) of 1.4 g/(m² day) at 90%RH had a structure that contained a core barrier film layer of nanocomposite MXD6 that makes up roughly 34% of the total film thickness, with the remainder of the film material consisting of maleic anhydride grafted polyolefin tie layers and LDPE skin layers. The OTR of the films changed as the relative humidity of the test environment was varied from 0 to 90%. However, for the pilot-scale trial it was necessary to reduce the target thickness of the core nylon barrier layer to 22% due to layer-to-layer melt flow instabilities that occurred during processing. The barrier properties of the multi-layer co-extruded films were highly dependant on overall film thickness. The highest performing oxygen barrier pilot-scale film had an OTR of 0.3 cm³/(m² day) (60%RH) and a WvTR of 2.4 g/(m² day) (90%RH) with a core nylon layer of 1.5 mil and a total thickness of 7.7 mil. Correlation of the layer thicknesses to the barrier and mechanical properties of the pilot-scale multilayer films indicated that an increased nanocomposite core layer thickness improved the oxygen barrier performance and decreased film elongation while improving the tear resistance of the films.     

High performance nitrile copolymers for polymer electrolyte membrane fuel cells

This paper reports the fuel cells (DMFC and PEMFC) performance using sulfonated poly(arylene ether ether nitrile) (SPAEEN) copolymers containing sulfonic acid group arranged in structurally different ways. The membrane electrode assembly (MEA) fabricated from SPAEEN containing 60 mol% of angled naphthalenesulfonic acid group (m-SPAEEN-60) had superior performance over those derived from pendent naphthalenesulfonic acid group (p-SPAEEN) or sulfonated hydroquinone (HQ-SPAEEN) in H₂/air and/or DMFC conditions. For example, the current density of the MEA using m-SPAEEN-60 at 0.5 V and 2.0 M methanol was 250 mA/cm², whereas the current densities of the MEAs using p-SPAEEN-50 and HQ-SPAEEN-56 were 185 and 190 mA/cm², respectively. In addition, compared with the sulfonated polysulfone (BPSH-35) and Nafion membranes, the copolymer containing nitrile group showed the improved cell performance. For example, the power density of the MEA using m-SPAEEN-60 at 250 mA/cm² and 2.0 M methanol was 125 mW/cm², whereas the power densities of the MEAs using sulfonated polysulfone (BPSH-35) and Nafion were 115 and 113 mW/cm², respectively. m-SPAEEN-60 showed stable cell performance during extended operation (>100 h).     

Platinum–polytyramine composite material with improved performances for methanol oxidation

Polytyramine (PTy) is shown to be a possible alternative to other conducting polymers as a support material for fuel cell electrocatalysts such as platinum. In this work, a Pt–PTy composite was prepared via potentiodynamic deposition of polytyramine on graphite substrate, followed by the electrochemical deposition of Pt nanoparticles. The material obtained by this straightforward method exhibited, for platinum loadings as low as ca. 0.12 mg cm⁻², a specific electrochemically active surface area of the electrocatalyst of ca. 54 m² g⁻¹, together with a good electrocatalytic activity for methanol oxidation in acidic media, thus ensuring better efficiency of Pt utilization. The system Pt–PTy appears to be worthy of development for methanol fuel cell applications also because the results suggested that, when deposited as small particles in a PTy matrix, platinum is less sensitive to fouling during CH₃OH oxidation.     

Alkaline fuel cells: Calculating and comparing overall currents of hydrophobized cathodes with thin regular-structure and thick stochastic-structure active layers

A concept of active hydrophobized active layers with regular structure is introduced. In these layers, a hydrophobizer takes part in the development of gas pores representing a set of straight identical rods (cylinders) uniformly distributed over the active layer and extended in a direction perpendicular to the cathode surface. An advantage of cathodes with a thin regular-structure active layer is the reproducibility of their characteristics and a low content of platinum catalyst (up to tenth and even hundredth fractions of mg/cm²). A comparison of current characteristics of thin (with the thickness of several tens of μm) active layers with a regular structure and thick (with the thickness of several hundreds of μm) with the stochastic distribution of the hydrophobizer (with randomly distributed polytetrafluoroethylene) is made. For a fuel cell with an alkaline electrolyte (7 M KOH at 60°C), calculations show that at potentials below 0.5 V (RHE), the cathodes with thin regularstructure active layers demonstrate higher overall currents as compared with cathodes covered with thick active layers with a stochastic structure. However, the opposite trend is observed at potentials above 0.5 V. To increase the current in cathodes with thin regular-structure active layers, it is possible to, first, increase the active layer thickness and, second, decrease the size of hydrophobizer grains in them.