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3 Technological Advances in Electrolyte Development for DMFCs The electrolytes that were first used in DMFC devices in the 1950s consisted of a concentrated alkaline solution for example, KOH which contained dissolved methanol [3, 25, 26, 93, 94]. Although some attempts were also carried out with anion exchange membranes onto which the electrodes were pressed [95], using an approach similar to the modern PEMFCs, the best results in terms of output power were achieved with 5 M KOH [94]. Alkaline instead of protonic electrolytes were initially selected because methanol oxidation in alkaline media is faster than in the presence of acidic electrolytes [95].

The number of anodic formulations investigated reduced consistently. More attention addressed the behavior of the catalyst inserted in a practical MEA in a single cell. It was observed that operation at high anode potentials often caused Ru dissolution and migration through the membrane to the cathode [43]. The extensive use of combinatorial catalyst discovery studies in the 1990s suggested that multifunctional catalysts could be of significant importance [44]. It had been established in the 1970s and 1980s that the activity of a methanol oxidation catalyst depends on several factors, including catalyst formulation, support, electrode structure and operating conditions.

In a polarization curve, the onset of diffusional limitations occurs when the rate of reactant supply is lower than the rate of its electrochemical consumption. Thus, if the anode is sufficiently active to oxidize methanol electrochemically to CO2 at a rate comparable to or higher than the rate of the methanol supply, the methanol concentration gradient between anode/electrolyte and cathode/electrolyte interfaces could be reduced significantly [11, 88, 117]. Membranes that are very thick are effective barriers for reducing methanol crossover; conversely, an increase in thickness causes an increase of ohmic overpotentials.

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