Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

PtSnIr/C anode electrocatalysts: Promoting effect in direct ethanol fuel cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH 2, PtO 2, SnO 2 and IrO 2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded. © 2012 Sociedade Brasileira de Química.

PtSnIr/C Anode Electrocatalysts: Promoting Effect in Direct Ethanol Fuel Cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH2, PtO2, SnO2 and IrO2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded.

PtSnIr/C anode electrocatalysts: promoting effect in direct ethanol fuel cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH2, PtO2, SnO2 and IrO2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded.

Capillary siphons and their application in the fuel delivery system of direct methanol fuel cells

The objective of the work is to develop a fuel delivery system for potable direct methanol fuel cell. Currently, one of the most fundamental limitations of direct methanol fuel cells is that the fuel supplied to the anode of the DMFC must be a very dilute aqueous methanol solution (usually 0.5∼1.5 M). If a DMFC is filled with a dilute aqueous methanol solution, the fuel cell operation time per refuel would be very short, which would considerably diminish the advantage of a DMFC over a conventional battery. To overcome this difficulty, a complex fuel delivery system based on the modern micro system technology was proposed by the author. The proposed fuel delivery system would include micro-pumps, a methanol sensor, and a control unit. The fuel delivery system adds considerable costs to the fuel cell system and consume considerable amount of electricity from the fuel cell, which in turn significantly reduces the net power output of the fuel cell. As a result, the DMFC would have tremendous difficulty to compete with the conventional battery technology in terms of costs and power output. ^ This work presents a novel passive fuel delivery system for direct methanol fuel cells. In this particular system, a methanol fuel and an aqueous methanol solution are stored separately in two containers and a wick is disposed between the two containers in a siphon fashion, with the container of the aqueous methanol solution communicating with the anode of the DMFC. Methanol is siphoned from the methanol container to the aqueous solution container in-situ when the methanol in the aqueous methanol solution is consumed during the operation of the fuel cell. Through a proper selection of the wick and the containers, the methanol concentration near the anode of the DMFC could be maintained within a preferable range. ^

Ashort reviewondirect borohydride fuel cells

Direct borohydride fuel cells (DBFC) use aqueous alkaline sodium borohydride(NaBH4) as anode fuel to generate electric power with either oxygen or hydrogen peroxide as oxidant. The DBFCs are projected to be very handy for portable power appliances such as laptops and mobile phones in addition to their use in extreme conditions such as underwater and portable military applications. This short review discusses the progress in DBFC research based on electrode materials and membranes.

Excellent performance of Pt-free cathode in alkaline direct methanol fuel cell at room temperature

We report the room temperature cell performance of alkaline direct methanol fuel cells (ADMFCs) with nitrogen-doped carbon nanotubes (NCNTs) as cathode materials. NCNTs show excellent oxygen reduction reaction activity and methanol tolerance in alkaline medium. The open-circuit-voltage (OCV) as well as the power density of ADMFCs first increases and then saturates with NCNT loading. Similarly, the OCV initially increases and reaches saturation with the increase in the concentration of methanol feed stock. Overall, NCNTs exhibit excellent catalytic activity and stability with respect to Pt based cathodes.

Two-Phase Flow In Anode Flow Field Of A Small Direct Methanol Fuel Cell In Different Gravities

An in-situ visualization of two-phase flow inside anode flow bed of a small liquid fed direct methanol fuel cells in normal and reduced gravity has been conducted in a drop tower. The anode flow bed consists of 11 parallel straight channels. The length, width and depth of single channel, which had rectangular cross section, are 48.0, 2.5 and 2.0 mm, respectively. The rib width was 2.0 mm. The experimental results indicated that when the fuel cell orientation is vertical, two-phase flow pattern in anode channels can evolve from bubbly flow in normal gravity into slug flow in microgravity. The size of bubbles in the reduced gravity is also bigger. In microgravity, the bubbles rising speed in vertical channels is obviously slower than that in normal gravity. When the fuel cell orientation is horizontal, the slug flow in the reduced gravity has almost the same characteristic with that in normal gravity. It implies that the effect of gravity on two-phase flow is small and the bubbles removal is governed by viscous drag. When the gas slugs or gas columns occupy channels, the performance of liquid fed direct methanol fuel cells is failing rapidly. It infers that in long-term microgravity, flow bed and operating condition should be optimized to avoid concentration polarization of fuel cells.

Experimental Investigation of Performance of a Miniature Direct Methanol Fuel Cell in Short-Term Microgravity

Experimental study of a liquid fed direct methanol fuel cell has been conducted in different gravity environments. A small single cell with 5 cm x 5 cm active area has single serpentine channel on the graphite cathode polar plate and 11 parallel straight channels on the graphite anode flow bed. Cell voltage and current have been measured and two-phase flow in anode channels has been in situ visually observed. The experimental results indicate that the effect of gravity on power performance of the direct methanol fuel cell is large when the concentration polarization governs fuel cells operation. Gravitational effect becomes larger at higher current density. Increasing methanol feeding molarity is conducive to weaken the influence of gravity on performance of liquid fed direct methanol fuel cells. Increasing feeding flow rate of methanol solution from 6 to 15 ml/min could reduce the size of carbon dioxide bubbles, while the influence of gravity still exist. Transport phenomena inside direct methanol fuel cells in microgravity is also analyzed and discussed.

Chitosan/heteropolyacid composite membranes for direct methanol fuel cell

As inorganic proton conductors. phosphomolybdic acid (PMA), phosphotungstic acid (PWA) and silicotungstic acid (SiWA) are extremely attractive for proton-conducting composite membranes. An interesting phenomenon has been found in our previous experiments that the mixing of chitosan (CS) solution and different heteropolyacids (HPAs) leads to strong electrostatic interaction to form insoluble complexes. These complexes in the form of membrane (CS/PMA, CS/PWA and CS/SiWA composite membranes) have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Therefore, HPAs can be immobilized within the membranes through electrostatic interaction, which overcomes the leakage problem from membranes.

Influence of electrode structure on the performance of a direct methanol fuel cell

Direct methanol fuel cells (DMFCs) consisting of multi-layer electrodes provide higher performance than those with the traditional electrode. The new electrode structure includes a hydrophilic thin film and a traditional catalyst layer. A decal transfer method was used to apply the thin film to the Nafion(R) membrane. Results show that the performance of a cell with the hydrophilic thin film is obviously enhanced. A cell with the optimal thin film electrode structure operating at I M CH3OH, 2 atm oxygen and 90degreesC yields a current density of 100 mA/cm(2) at 0.53 V cell voltage. The peak power density is 120 mW/cm(2). The performance stability of a cell in a short-term life operation was also increased when the hydrophilic thin film was employed. (C) 2002 Elsevier Science B.V. All rights reserved.