Mordenite-incorporated PVA-PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm2 is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm2 with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.

Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.

A new mixed-matrix membrane for DMFCs

A new mixed-matrix membrane based on stabilized phosphotungstic acid (PTA) incorporated to chitosan (CS)-hydroxy ethyl cellulose (HEC) for application in direct methanol fuel cells (DMFCs) is reported. Membranes are characterised using Fourier Transform Spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and their mechanical properties are evaluated. The PTA content in the CS-HEC blend and its influence on proton conductivity, water/methanol sorption, and methanol cross-over in the DMFC is studied. The DMFC with 3 wt. % stabilized PTA-CS-HEC mixed-matrix membrane delivers peak power-density of 58 mW/cm(2) at a load current-density of 210 mA/cm(2) with a lower methanol cross-over than that observed for a DMFC operating with a Nafion membrane electrolyte.

A Methanol-Tolerant Carbon-Supported Pt-Au Alloy Cathode Catalyst for Direct Methanol Fuel Cells and Its Evaluation by DFT

A Pt-Au alloy catalyst of varying compositions is prepared by codeposition of Pt and Au nanoparticles onto a carbon support to evaluate its electrocatalytic activity toward an oxygen reduction reaction (ORR) with methanol tolerance in direct methanol fuel cells. The optimum atomic weight ratio of Pt to Au in the carbon-supported Pt-Au alloy (Pt-Au/C) as established by cell polarization, linear-sweep voltammetry (LSV), and cyclic voltammetry (CV) studies is determined to be 2:1. A direct methanol fuel cell (DMFC) comprising a carbon-supported Pt-Au (2:1) alloy as the cathode catalyst delivers a peak power density of 120 mW/cm2 at 70 °C in contrast to the peak power density value of 80 mW/cm2 delivered by the DMFC with carbon-supported Pt catalyst operating under identical conditions. Density functional theory (DFT) calculations on a small model cluster reflect electron transfer from Pt to Au within the alloy to be responsible for the synergistic promotion of the oxygen-reduction reaction on a Pt-Au electrode.

PVA-PSSA Membrane with Interpenetrating Networks and its Methanol Crossover Mitigating Effect in DMFCs

A membrane with interpenetrating networks between poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) coupled with a high proton conductivity is realized and evaluated as a proton exchange membrane electrolyte for a direct methanol fuel cell (DMFC). Its reduced methanol permeability and improved performance in DMFCs suggest the new blend as an alternative membrane to Nafion membranes. The membrane has been characterized by powder X-ray diffraction, scanning electron microscopy, time-modulated differential scanning calorimetry, and thermogravimetric analysis in conjunction with its mechanical strength. The maximum proton conductivity of 3.3×10−2 S/cm for the PVA–PSSA blend membrane is observed at 373 K. From nuclear magnetic resonance imaging and volume localized spectroscopy experiments, the PVA–PSSA membrane has been found to exhibit a promising methanol impermeability, in DMFCs. On evaluating its utility in a DMFC, it has been found that a peak power density of 90 mW/cm2 at a load current density of 320 mA/cm2 is achieved with the PVA–PSSA membrane compared to a peak power density of 75 mW/cm2 at a load current density of 250 mA/cm2 achievable for a DMFC employing Nafion membrane electrolyte while operating under identical conditions; this is attributed primarily to the methanol crossover mitigating property of the PVA–PSSA membrane.

PVA-SSA-HPA Mixed-Matrix-Membrane Electrolytes for DMFCs

Stabilized forms of heteropolyacids (HPAs), namely phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA), are incorporated into poly (vinyl alcohol) (PVA) cross-linked with sulfosuccinic acid (SSA) to form mixed-matrix membranes for application in direct methanol fuel cells (DMFCs). Bridging SSA between PVA molecules not only strengthens the network but also facilitates proton conduction in HPAs. The mixed-matrix membranes are characterized for their mechanical stability, sorption capability, ion-exchange capacity, and wetting in conjunction with their proton conductivity, methanol permeability, and DMFC performance. Methanol-release kinetics is studied ex situ by volume-localized NMR spectroscopy (employing point-resolved spectroscopy'') with the results clearly demonstrating that the incorporation of certain inorganic fillers in PVA-SSA viz., STA and PTA, retards the methanol-release kinetics under osmotic drag compared to Nafion, although PVA-SSA itself exhibits a still lower methanol permeability. The methanol crossover rate for PVA-SSA-HPA-bridged-mixed-matrix membranes decreases dramatically with increasing current density rendering higher DMFC performance in relation to a DMFC using a pristine PVA-SSA membrane. A peak power density of 150 mW/cm(2) at a load current density of 500 mA/cm(2) is achieved for the DMFC using a PVA-SSA-STA-bridged-mixed-matrix-membrane electrolyte. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3465653] All rights reserved.

Sodium-alginate-based proton-exchange membranes as electrolytes for DMFCs

Novel mixed-matrix membranes prepared by blending sodium alginate (NaAlg) with polyvinyl alcohol (PVA) and certain heteropolyacids (HPAs), such as phosphomolybdic acid (PMoA), phosphotungstic acid (PWA) and silicotungstic acid (SWA), followed by ex-situ cross-linking with glutaraldehyde (GA) to achieve the desired mechanical and chemical stability, are reported for use as electrolytes in direct methanol fuel cells (DMFCs). NaAlg-PVA-HPA mixed matrices possess a polymeric network with micro-domains that restrict methanol cross-over. The mixed-matrix membranes are characterised for their mechanical and thermal properties. Methanol cross-over rates across NaAlg-PVA and NaAlg-PVA-HPA mixed-matrix membranes are studied by measuring the mass balance of methanol using a density meter. The DMFC using NaAlg-PVA-SWA exhibits a peak power-density of 68 mW cm(-2) at a load current-density of 225 mA cm(-2), while operating at 343 K. The rheological properties of NaAlg and NaAlg-PVA-SWA viscous solutions are studied and their behaviour validated by a non-Newtonian power-law.

Modified-Pore-Filled-PVDF-Membrane Electrolytes for Direct Methanol Fuel Cells

The polyvinylidene fluoride (PVDF) membrane is modified by the chemical etchant-route employing a sodium naphthalene charge-transfer complex followed by impregnation with Nafion ionomer or polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) polymeric blend solutions by a dip-coating technique to form pore-filled-membrane electrolytes for application in direct methanol fuel cells (DMFCs). The number of coatings on the surface-modified PVDF membrane is varied between 5 and 15 and is found to be optimum at 10 layers both for Nafion and PVA-PSSA impregnations for effective DMFC performance. Hydrophilicity of the modified-membrane electrolytes is studied by determining average contact angle and surface-wetting energy. Morphology of the membranes is analyzed by a cross-sectional scanning electron microscope. The modified PVDF membrane electrolytes are characterized for their water-methanol sorption in conjunction with their mechanical properties, proton conductivity, and DMFC performance. Air permeability for the modified membranes is studied by a capillary-flow porometer. Methanol crossover flux across modified-PVDF-membrane electrolytes is studied by measuring the mass balance of methanol using a density meter. DMFCs employing membrane electrode assemblies with the modified PVDF membranes exhibit a peak power-density of 83 mW/cm(2) with Nafion impregnation and 59 mW/cm(2) for PVA-PSSA impregnation, respectively. Among the membranes studied here, stabilities of modified-pore-filled PVDF-Nafion and PVDF-PVA-PSSA membranes with 10-layers coat are promising for application in DMFCs. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3518774] All rights reserved.

An improved-performance liquid-feed solid-polymer-electrolyte direct methanol fuel cell operating at near-ambient conditions

Results on the performance of a 25 cm(2) liquid-feed solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFC), operating under near-ambient conditions, are reported. The SPE-DMFC can yield a maximum power density of c. 200 mW cm(-2) at 90 C while operating with 1 M aqueous methanol and oxygen under ambient pressure. While operating the SPE-DMFC under similar conditions with air, a maximum power density of ca. 100 mW cm(-2) is achieved. Analysis of the electrode reaction kinetics parameters on the methanol electrode suggests that the reaction mechanism for methanol oxidation remains invariant with temperature. Durability data on the SPE-DMFC at an operational current density of 100 mA cm(-2) have also been obtained.

A self-supported 40W direct methanol fuel cell system

A self-supported 40W Direct Methanol Fuel Cell (DMFC) system has been developed and performance tested. The auxiliaries in the DMFC system comprise a methanol sensor, a liquid-level indicator, and fuel and air pumps that consume a total power of about 5W. The system has a 15-cell DMFC stack with active electrode-area of 45 cm(2). The self-supported DMFC system addresses issues related to water recovery from the cathode exhaust, and maintains a constant methanol-feed concentration with thermal management in the system. Pure methanol and water from cathode exhaust are pumped to the methanol-mixing tank where the liquid level is monitored and controlled with the help of a liquid-level indicator. During the operation, methanol concentration in the feed solution at the stack outlet is monitored using a methanol sensor, and pure methanol is added to restore the desired methanol concentration in the feed tank by adding the product water from the cathode exhaust. The feed-rate requirements of fuel and oxidant are designed for the stack capacity of 40W. The self-supported DMFC system is ideally suited for various defense and civil applications and, in particular, for charging the storage batteries.

Bio-Composite Membrane Electrolytes for Direct Methanol Fuel Cells

A new class of bio-composite polymer electrolyte membranes comprising chitosan (CS) and certain biomolecules in particular, plant hormones such as 3-indole acetic acid (IAA), 4-chlorophenoxy acetic acid (CAA) and 1-naphthalene acetic acid (NAA) are explored to realize proton-conducting bio-composite membranes for application in direct methanol fuel cells (DMFCs). The sorption capability, proton conductivity and ion-exchange capacity of the membranes are characterized in conjunction with their thermal and mechanical behaviour. A novel approach to measure the permeability of the membranes to both water and methanol is also reported, employing NMR imaging and volume localized NMR spectroscopy, using a two compartment permeability cell. A DMFC using CS-IAA composite membrane, operating with 2M aqueous methanol and air at 70 degrees C delivers a peak power density of 25 mW/cm(2) at a load current density of 150 mA/cm(2). The study opens up the use of bio-compatible membranes in polymer-electrolyte-membrane fuel cells. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.030111jes] All rights reserved.

Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.