Direct Methanol Fuel Cells DMFC

Note it is the protons that migrate from the negative to the positive electrode and not the methanol molecules, and it is this feature that permits the use of a proton-exchange membrane. 

A number of challenges have been identified with the DMFC. In brief, these are as follows. 

These reactions occur at a very slow rate on pure platinum and this has resulted in a large research effort to discover more active electrocatalysts. At present, platinum—ruthenium offers the best performance. Ruthenium adsorbs water more readily than platinum and the resulting species, Ru—OHads, assists the removal of carbon monoxide from neighbouring platinum sites. Despite this beneficial effect of ruthenium, still more efficient electrocatalysts are required to enhance the power delivered by DMFCs, especially if the system is to compete favourably with hydrogen—air PEMFCs. 

Equation (1.19) clearly implies the efficiency of methanol as a fuel because 6 electrons are produced per methanol molecule. However, as mentioned in Sect. 1.2.1.3, carbon dioxide will react with hydroxide resulting in the formation of the carbonate, which decreases the hydroxide concentration. The major problem for alkaline DMFC is that no carbon dioxide is produced as a product as all of the CO2 reacts with the hydroxide i.e.. 

these alkaline DMFC are practically discarded. Therefore, the main focus is on the polymer electrolyte membrane DMFC. 

The anode and cathode reactions for PEM DMFC are given as follows  

The electrons move via external circuit and the proton migrates through the electrolyte towards the cathode side. 

CH20H / Hydrogen stripping (removal of hydrogen atom) 

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The schematic diagram of the liquid-feed direct methanol fuel cell (DMFC) is shown in Figure 13.1. 

Fuel cells can run on fuels other than hydrogen. In the direct methanol fuel cell (DMFC), a dilute methanol solution ( 3%) is fed directly into the anode, and a multistep process causes the liberation of protons and electrons together with conversion to water and carbon dioxide. Because no fuel processor is required, the system is conceptually vei"y attractive. However, the multistep process is understandably less rapid than the simpler hydrogen reaction, and this causes the direct methanol fuel cell stack to produce less power and to need more catalyst. 

The dynamic behavior of fuel cells is of importance to insure the stable operation of the fuel cells under various operating conditions. Among a few different fuel cell types, the direct methanol fuel cell (DMFC) has been known to have advantages especially for portable... 

The electrocatalytic oxidation of methanol has been widely investigated for exploitation in the so-called direct methanol fuel cell (DMFC). The most likely type of DMFC to be commercialized in the near future seems to be the polymer electrolyte membrane DMFC using proton exchange membrane, a special form of low-temperature fuel cell based on PEM technology. In this cell, methanol (a liquid fuel available at low cost, easily handled, stored, and transported) is dissolved in an acid electrolyte and burned directly by air to carbon dioxide. The prominence of the DMFCs with respect to safety, simple device fabrication, and low cost has rendered them promising candidates for applications ranging from portable power sources to secondary cells for prospective electric vehicles. Notwithstanding, DMFCs were... 

PEMFC)/direct methanol fuel cell (DMFC) cathode limit the available sites for reduction of molecular oxygen. Alternatively, at the anode of a PEMFC or DMFC, the oxidation of water is necessary to produce hydroxyl or oxygen species that participate in oxidation of strongly bound carbon monoxide species. Taylor and co-workers [Taylor et ah, 2007b] have recently reported on a systematic study that examined the potential dependence of water redox reactions over a series of different metal electrode surfaces. For comparison purposes, we will start with a brief discussion of electronic structure studies of water activity with consideration of UHV model systems. 

Caillard A, Coutanceau C, Brault P, Mathias J, Leger JM. 2006. Structure of Pt/C and PtRu/C catalytic layers prepared by plasma sputtering and electric performance in direct methanol fuel cells (DMFC). J Power Sources 162 66-73. 

The Pt/Ru catalyst is the material of choice for the direct methanol fuel cell (DMFC) (and hydrogen reformate) fuel cell anodes, and its catalytic function needs to be completely understood. In the hrst approximation, as is now widely acknowledged, methanol decomposes on Pt sites of the Pt/Ru surface, producing chemisorbed CO that is transferred via surface motions to the active Pt/Ru sites to become oxidized to CO2... 

For isolating the overpotential of the working electrode, it is common practice to admit hydrogen to the counter-electrode (the anode in a PEMFC the cathode in a direct methanol fuel cell, DMFC) and create a so-called dynamic reference electrode. Furthermore, the overpotential comprises losses associated with sluggish electrochemical kinetics, as well as a concentration polarization related to hindered mass transport ... 

The electrodes in the direct methanol fuel cell (DMFC) (i.e. the anode for oxidising the fuel and the cathode for the reduction of oxygen) are based on finely divided Pt dispersed onto a porous carbon support, and the electro-oxidation of methanol at a polycrystalline Pt electrode as a model for the DMFC has been the subject of numerous electrochemical studies dating back to the early years ot the 20th century. In this particular section, the discussion is restricted to the identity of the species that result from the chemisorption of methanol at Pt in acid electrolyte. This is principally because (i) the identity of the catalytic poison formed during the chemisorption of methanol has been a source of controversy for many years, and (ii) the advent of in situ IR culminated in this controversy being resolved. 

There are six different types of fuel cells (Table 1.6) (1) alkaline fuel cell (AFC), (2) direct methanol fuel cell (DMFC), (3) molten carbonate fuel cell (MCFC), (4) phosphoric acid fuel cell (PAFC), (5) proton exchange membrane fuel cell (PEMFC), and (6) the solid oxide fuel cell (SOFC). They all differ in applications, operating temperatures, cost, and efficiency. 

The methanol oxidation reaction has been heavily studied in recent years due to interest in direct methanol fuel cells (DMFCs).4 90 The methanol oxidation halfreaction in a direct methanol fuel cell is... 

Direct hydration, of ethylene, 10 538 Direct hydrogenation, 6 827 Direct immunosensors, 14 154 Direct ingot (dingot) method, 25 409 Direct initiation, 14 270 Direct injection (DI) diesel engines, 12 421 Direct inlet injection, gas chromatography, 6 383, 415-416 Directional couplers, 17 446 Directional drilling techniques, in sulfur extraction, 23 572 Directive 89/107/EEC (EU), 12 36 Direct liquefaction, 6 827 Direct marketing, technical service personnel and, 24 343 Direct metal nitridation, 17 211-213 aerosol flow reactor, 17 211-212 Direct methanol fuel cells (DMFC),... 

This survey focuses on recent developments in catalysts for phosphoric acid fuel cells (PAFC), proton-exchange membrane fuel cells (PEMFC), and the direct methanol fuel cell (DMFC). In PAFC, operating at 160-220°C, orthophosphoric acid is used as the electrolyte, the anode catalyst is Pt and the cathode can be a bimetallic system like Pt/Cr/Co. For this purpose, a bimetallic colloidal precursor of the composition Pt50Co30Cr20 (size 3.8 nm) was prepared by the co-reduction of the corresponding metal salts [184-186], From XRD analysis, the bimetallic particles were found alloyed in an ordered fct-structure. The elecbocatalytic performance in a standard half-cell was compared with an industrial standard catalyst (bimetallic crystallites of 5.7 nm size) manufactured by co-precipitation and subsequent annealing to 900°C. The advantage of the bimetallic colloid catalysts lies in its improved durability, which is essential for PAFC applicabons. After 22 h it was found that the potential had decayed by less than 10 mV [187],... 

Direct methanol fuel cells (DMFCs) can run on methanol without a reformer. But, practical, affordable DMFCs for cars and trucks may still be years away. 

In addition to these smaller applications, fuel cells can be used in portable generators, such as those used to provide electricity for portable equipment. Thousands of portable fuel cell systems have been developed and operated worldwide, ranging from 1 watt to 1.5 kilowatts in power. The two primary technologies for portable applications are polymer electrolyte membrane (PEM) and direct methanol fuel cell (DMFC) designs. 

All fuel cells for use in vehicles are based on proton-exchange-membrane fuel cell (PEMFC) technology. The methanol fuel-processor fuel cell (FPFC) vehicle comprises an on-board fuel processor with downstream PEMFC. On-board methanol reforming was a development focus of industry for a number of years until around 2002. Direct-methanol fuel cells (DMFC) are no longer considered for the propulsion of commercial vehicles in the industry (see also Chapter 13). 

Direct-methanol fuel cells (DMFCs) have attracted considerable attention for certain mobile and portable applications, because of their high specific energy density, low poison emissions, easy fuel handling, and miniaturization [129,130], However, the methanol permeation through electrolyte membranes (usually called methanol cross-over) in DMFCs still is one of the critical problems hindering the commercialization [131,132], Nafion , a... 

Anode Investigations using cyclovoltammetry confirm an important effect of surface oxides (see Vols. 3, 4). A known example of the different anodic activity is the poisoning of platinum by adsorbed carbon monoxide species, for example, in the direct methanol fuel cell (DMFC),... 

Cho, K.-Y, Jung, H.-Y., Choi, N.-S., Sung, S.-H., Park, J.-K., Choi, J.-H. and Sung, Y.-E. 2005. A coated Nafion membrane with a PVdF copolymer/ Nafion blend for direct methanol fuel cells (DMFCs). Solid State Ionics 176 3027-3030. 

In electrochemical systems, metal meshes have been widely used as the backing layers for catalyst layers (or electrodes) [26-29] and as separators [30]. In fuel cells where an aqueous electrolyte is employed, metal screens or sheets have been used as the diffusion layers with catalyst layers coated on them [31]. In direct liquid fuel cells, such as the direct methanol fuel cell (DMFC), there has been research with metal meshes as DLs in order to replace the typical CFPs and CCs because they are considered unsuitable for the transport and release of carbon dioxide gas from the anode side of the cell [32]. 

A particular version of the PEFC is the direct methanol fuel cell (DMFC). As the name implies, an aqueous solution of methanol is used as fuel instead of the hydrogen-rich gas, eliminating the need for reformers and shift reactors. The major challenge for the DMFC is the crossover of methanol from the anode compartment into the cathode compartment through the membrane that poisons the electrodes by CO. Consequently, the cell potentials and hence the system efficiencies are still low. Nevertheless, the DMFC offers the prospect of replacing batteries in consumer electronics and has attracted the interest of this industry. 

The efficiency of PEMFCs ranges from about 40 to 50%, and operating temperature is about 255 K. The PEMFCs and direct methanol fuel cells (DMFCs) are considered to be promising power sources, especially for transportation applications. The PEMFCs with potentially much higher efficiencies and almost zero emissions offer an attractive alternative to the internal combustion engines for automotive applications. This fuel cell has many important attributes such as high efficiency, clean, quiet, low-temperature operation, capable of quick start-up, no liquid electrolyte and simple cell design (Hu et al., 2004). 

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