Confined PFSA-zeolite composite membrane for self-humidifying fuel cell

Perfluorosulfonic acid (PFSA) polyelectrolyte confined in subnanoliter volume within zeolite cladded walls exhibits higher glass transition temperature and excellent tolerance to high-temperature fuel cell operation under dry conditions, generating an order of magnitude higher power density than standard PEMFC.     

Reinforced and self-humidifying composite membrane for fuel cell applications

A novel preparation method for a composite proton exchange membrane with reinforced strength and self-humidifying property was developed. Using self-assembly method, highly dispersed poly(diallyldimethylammonium chloride) (PDDA) stabilized Pt nanoparticles were mounted onto the pores of poly(tetrafluoroethylene) (PTFE) porous film to serve the self-humidifying purpose. With Pt nanoparticles fixed on the PTFE pores, the potential problem of any short circuit because of the use of metal nanoparticles can be prevented. Pt-PDDA/PTFE substrate in the composite membrane can enhance the mechanical strength of the membrane and distribute self-humidifying layer adjacent to the anode side. Compared with the cells fabricated with conventional Nafion^® and PTFE/Nafion membranes, the performance of the cells with this composite membrane is dramatically improved under dry conditions. Electrochemical impedance spectroscopy technique revealed that these self-humidifying composite membranes could minimize membrane conductivity loss under dry conditions.     

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.     

Sulfonated poly(fluorenyl ether ketone) membrane prepared via direct polymerization for PEM fuel cell application

Sulfonated poly(fluorenyl ether ketone)s with inherent viscosity ranging from 0.68 to 0.93 dL/g were directly synthesized by aromatic nucleophilic polycondensation of bisphenol fluorene with various ratios of sulfonated difluorobenzophenone to difluorobenzophenone. The synthesized polymers were characterized by ¹H NMR method and elemental analysis. The polymers were tested to be soluble in dipolar aprotic solvents such as DMAc, DMF and DMSO and can be readily cast into tough films. These films showed highly thermal degradation temperature, glass transition temperature and excellent water affinity as well as excellent proton conductivity. The polymers showed a promising proton membrane material for PEM fuel cell application.     

Fluorene-containing block sulfonated poly(ether ether ketone) as proton-exchange membrane for PEM fuel cell application

A series of sulfonated block poly(ether ether ketone)s with different sulfonic acid group clusters were successfully synthesized by nucleophilic displacement condensation. Membranes were accordingly cast from their DMSO solutions, and fully characterized by determining the ion-exchange capacity, water uptake, proton conductivity, dimensional stabilities and mechanical properties. The experimental results showed that the main properties of the membrane can be tailored by changing the cluster size of sulfonic acid groups. The membrane of block-7c(40) has good mechanical, oxidative and dimensional stabilities together with high proton conductivity (5.09 × 10⁻² S cm⁻¹) at 80 °C under 100% relative humidity. The membranes also possess excellent thermal and dimensional stabilities. These polymers are potential and promising proton conducting membrane material for PEM full cell applications.     

Electrochemical noise diagnostics of PEM fuel cell stack for micro-cogeneration application

Journal of Solid State Electrochemistry - Electrochemical noise (EN) generated by a 3500 W PEM fuel cell stack (50 cells) has been measured during micro-cogeneration durability tests. The...     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

Exfoliated Pt-clay/Nafion nanocomposite membrane for self-humidifying polymer electrolyte fuel cells

Monolayers of Pt nanoparticles of diameters of 2-3 nm with a high crystallinity were successfully anchored onto exfoliated nanoclay surfaces using a novel chemical vapor deposition process. Chemical bonding of Pt to the oxygen on the clay surface ensured the stability of the Pt nanoparticles, and hence, no leaching of Pt particles was observed after a prolonged ultrasonication and a rigorous mechanical agitation of Pt-clay in the Nafion solution during the membrane casting process. Systematic analysis using WAXD and TEM showed that the recasting process produced a new self-humidifying exfoliated Pt-clay/Nafion nanocomposite membrane with a high crystallinity and proton conductivity. In situ water production for humidification of the dry membranes without any external humidification was characterized by a combined water uptake and FTIR analysis of the as-prepared membrane after a single cell testing without using electrodes. The power density at 0.5 V of a single cell made of a Pt-clay/Nafion nanocomposite membrane was 723 mW/cm2, which is 170% higher than that made of a commercial Nafion 112 membrane of similar thickness. No compromise in mechanical properties was observed.     

Synthesis,characterization, and transport properties of Nafion-polypyrrole membrane for direct methanol fuel cell (DMFC) application

Journal of Solid State Electrochemistry - Due to their distinctive chemical, electronic, and environmental properties, polypyrrole is used as a blocking barrier for methanol leakage in direct...     

Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes

Electrospun materials have been gaining great interest in the energy sector. Their tunability and robustness make them highly attractive, particularly for proton-exchange membrane fuel cell (PEMFC) electrodes. Conventional PEMFC electrodes, prepared by either spraying, painting, or slot-die coating, have not yet met the needs of large-scale PEMFC use. Electrospinning of fibrous materials has already shown great promise as an alternative methodology for electrode fabrication. Electrospinning has been used in fuel cell electrodes through two primary means: (1) segmented carbon or inorganic fibers to serve as precious metal catalyst support, and (2) high aspect ratio polymer/particle fibers to serve directly as the electrode. The use of electrospun fibrous electrodes has led to improved PEMFC durability and increased power output at low catalyst loadings, both of which are of paramount importance to large-scale commercialization of PEMFC electric vehicles.     

Thermal analysis of sulfonated polymers tested as polymer electrolyte membrane for PEM fuel cells

An aromatic polymer, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) was sulfonate with different sulfonation degrees (30, 50, and 75?% theoretical degree) to obtain an electrolytic polymer suitable as proton exchange membrane for fuel cells. Thermal behaviors of sulfonated PPO were tested by differential scanning calorimetry and thermogravimetry. The sulfonation degrees were correlated with glass transitions temperatures (T _g) and the percent of weight loss. One notices a good fitting between sulfonation degree and the percent of weight loss thanks splitting of sulfonic moieties but it is not the same for glass transition temperatures that have a random variation.     

Potential application of anion-exchange membrane for hydrazine fuel cell electrolyte

A platinum electrocatalyst layer was directly bound to a perfluorinated anion-exchange membrane (AEM) by the electroless plating method and used for the characterization of AEM as a polymer electrolyte membrane for a direct hydrazine fuel cell. The crossover amount of hydrazine through AEM was much lower than that through the cation-exchange membrane (CEM) that did not depend on the applied current density. The fuel cell performance was far superior when using AEM than when using CEM.     

Molecular oxygen reduction in PEM fuel cell conditions: ToF-SIMS analysis of co-based electrocatalysts

A series of Co-based electrocatalysts for oxygen reduction in acid media has been prepared using two different Co precursors: cobalt acetate (CoAc) and a cobalt porphyrin (CoTMPP). These catalysts have been analyzed by ToF-SIMS to obtain information on the number and the structure of catalytic active sites in these materials. The results are compared with the results of a similar analysis already performed on a series of Fe-based electrocatalysts (J. Phys. Chem. B 2002, 106, 8705) also prepared with two different Fe precursors: iron acetate (FeAc) and an iron porphyrin (ClFeTMPP). The interpretation of ToF-SIMS data for Fe-based catalysts allowed us to conclude that whatever the Fe precursor was, the same catalytic sites (FeN2/C and FeN4/C, with their respective dominant ToF-SIMS signatures: FeN2C4+ and FeN4C8+ ions) were found. The comparison of the ToF-SIMS data with the activity of those catalysts led to the conclusion that the FeN2C catalytic site was more active than FeN4/C. When the same procedure is applied to ToF-SIMS data measured for Co-based catalysts, the following conclusions are drawn: (i) as for Fe precursors, both Co precursors also give similar results; (ii) as for Fe-based catalysts, the same four families of MetalNxCy+ ions, with 1, 2, 3, and 4 nitrogen atoms, are also found in the spectra of Co-based catalysts, but there is no dominant CoNxCy+ ion signature; (iii) only CoN4/C can be ascertained on the basis of ToF-SIMS measurements. There is no strong support from ToF-SIMS measurements for (or against) the existence of CoN2/C in Co-based catalysts as there is for FeN2/C in Fe-based catalysts; (iv) contrary to Fe-based catalysts, all catalytic sites (if there are any besides CoN4/C) are about equally active in Co-based electrocatalysts.     

Anti-flooding cathode catalyst layer for high performance PEM fuel cell

Water management in cathode catalyst layer (CCL) plays an important role in the PEM fuel cell operation. A novel anti-flooding CCL is developed with the addition of oxygen permeable and hydrophobic dimethyl silicone oil (DSO) into the catalyst layer (CL) to improve the water balance and oxygen transport within the cathode. With the addition of 0.5 mg cm^?2 DSO in the CCL, the ability of water management has been enhanced greatly compared to that with a normal cathode. Electrochemical impedance spectroscopy has been employed to characterize the electrochemical behavior of the single fuel cell. The results show that the increased hydrophobicity of the CCL by DSO modification effectively expels water out of the voids of CCL. In addition, DSO in the CCL enhances oxygen accessibility to the CCL, thus improving the performance of the PEM fuel cell significantly.     

Proton exchange membrane with hydrophilic capillaries for elevated temperature PEM fuel cells

Novel water-retention proton exchange membrane of Nafion-phosphotungstic acid/mesoporous silica with hydrophilic capillaries has been fabricated to improve the elevated temperature performance of the PEM fuel cells. Due to the hydrophilic capillarity of the HPW/meso-SiO₂ mesoporous structure, the Nafion-HPW/meso-SiO₂ composite membrane retained 23.7 wt% of water after being dried in 100 °C for 2 h and then exposed in 25 RH% gas for 2 h. As a result, under the condition of elevated temperature of 120 °C and low humidity of 25 RH%, the Nafion-HPW/meso-SiO₂ composite membrane showed a steady performance.     

Synthesis and characterization of SPE membrane based on sulfonated FEP‐g‐acrylic acid by radiation induced graft copolymerization for PEM fuel cell

A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO₃H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO₃H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO₃H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H₂/O₂ fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd.     

Copper ring-disk microelectrodes: fabrication, characterization, and application as an amperometric detector for capillary columns

A novel approach to the fabrication of metal ring-disk (RD) microelectrodes is presented that employs flexible chemical vapor deposition (CVD) and electrode modification techniques. Specifically, the development of a copper ring-disk microelectrode is described utilizing a combination of CVD coating, electroetching, and electroplating. Initially, a 25 μm diameter tungsten wire is concentrically coated by CVD with an insulating layer of silica, a layer of tungsten metal, and finally, a second outer layer of silica. The copper surface was prepared by first creating micrometer cavities by electrochemical etching the tungsten in hydroxide solutions followed by electrodeposition of copper from aqueous solutions of Cu(II). Each step of the process was characterized by scanning electron microscopy, optical microscopy, and cyclic voltammetry, demonstrating the preparation of a viable metal-based dual ring-disk microelectrode system. For the purpose of demonstrating the concept of introducing specific selectivity into the device, amperometric detection of galactose in 0.1 M NaOH was performed at +0.60 V in bulk solution and after flow injection analysis in a capillary column.     

Cogeneration of cyclohexylamine and electrical power using PEM fuel cell reactor

Cogeneration of cyclohexylamine (CHA) and electrical power using a PEM fuel cell reactor were performed by the selective reduction of nitrobenzene (NB). The maximum power density was 1.5 mW cm⁻² at a current density of 15 mA cm⁻² during cogeneration with the reduction of NB in ethanol. The current density varied from 1.6 to 24 mA cm⁻² with the change of external load. A selectivity of 57.3% to CHA, and a selectivity of 28.2% to aniline (AN), with 8.2% conversion of NB were obtained when the hydrogen flow rate was 20 ml min⁻¹ at 70 °C for 2 h. Effects of Pt catalyst loading and NB concentration on the behavior of cogeneration were also studied.     

Spontaneous oscillations of cell voltage, power density, and anode exit CO concentration in a PEM fuel cell

The spontaneous oscillations of the cell voltage and output power density of a PEMFC (with PtRu/C anode) using CO-containing H(2) streams as anodic fuels have been observed during galvanostatic operating. It is ascribed to the dynamic coupling of the CO adsorption (poisoning) and the electrochemical CO oxidation (reactivating) processes in the anode chamber of the single PEMFC. Accompanying the cell voltage and power density oscillations, the discrete CO concentration oscillations at the anode outlet of the PEMFC were also detected, which directly confirms the electrochemical CO oxidation taking place in the anode chamber during galvanostatic operating.