Over the past decade the topic of energy and environment has been ackno- edged among many people as a critical issue to be solved in 21st century since the Kyoto Protocol came into e?ect in 1997. Its political recognition was put forward especially at Heiligendamm in 2007, when the e?ect of carbon dioxide emission and its hazard in global climate were discussed and shared univ- sallyascommonknowledge.Controllingtheglobalwarmingintheeconomical framework of massive development worldwide through this new century is a very challenging problem not only among political, economical, or social c- cles but also among technological or scienti?c communities. As long as the humans depend on the combustion of fossil for energy resources, the waste heat exhaustion and CO emission are inevitable. 2 In order to establish a new era of energy saving and environment benign society, which is supported by technologies and with social consensus, it is important to seek for a framework where new clean energy system is inc- porated as infrastructure for industry and human activities. Such a society strongly needs innovative technologies of least CO emission and e?cient en- 2 ergy conversion and utilization from remaining fossil energies on the Earth. Energy recycling system utilizing natural renewable energies and their c- version to hydrogen may be the most desirable option of future clean energy society. Thus the society should strive to change its energy basis, from foss- consuming energy to clean and recycling energy.
In this book the authors focus on the ion and water transport characteristics in Nafion and other perfluorinated ionomer membranes that are recently attracting attention in various fields such as water electrolysis, mineral recovery, electrochemical devises and energy conversion. Methodology of measurements and data analysis is first presented that enables basic characterisation of transport parameters in the perfluorinated ionomer membranes. Cation exchange isotherm data are collected in binary cation systems, with the aim to see the behaviours of cationic species that exist with H+ in the membrane. Water transference coefficients, ionic transference numbers, ionic mobilities and other membrane transport parameters are measured in single and mixed counter cation systems using electrochemical methods. Diffusion coefficients of water and cations are also measured by pulsed-field-gradient spin-echo NMR (PGSE-NMR) at various temperatures in different kinds of perfluorinated ionomer membranes. The results are discussed in two perspectives. One is to predict the hydration state in perfluorosulfonated ionomer membranes in relation to the possible degradation of performances in fuel cells under contaminated conditions with foreign cations. An analytical formulation of membrane transport equations with proper boundary conditions is proposed, and using various parameters of membrane transport, a simple diagnosis of water dehydration problem is carried out. This analysis leads one to an effective control of fuel cell operation conditions, especially from viewpoint of proper water management. The others are to elucidate the ion and water transport mechanisms in the membrane in relation to polymer structures (e.g., different ion exchange capacity), and to propose a new design concept of polymer electrolyte membranes for fuel cell applications. Additionally for this purpose methanol and other alcohols are penetrated into the membrane, and alcohol permeability, membrane swelling, ionic conductivity and diffusion coefficients of water and CH3 are measured systematically for various kinds of membranes to cope with the problem of methanol crossover in direct methanol fuel cells (DMFCs).It is found that in order to realise a high ionic conductivity in the membrane, one should aim at a polymer structure through molecular design that takes into account the relative size of ions with a hydration shell against the size and atmosphere of ionic channels. For DMFC, a partially cross-linked polymer chain with high degree of hydrophilic ion transport paths based on phase-separated structures is recommended. Various possibilities of such polymer electrolytes are discussed.
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