Doping and defect structure of mixed-conducting ceramics for gas separation.

摘要

A worldwide energy crisis and increasing environmental concerns are strong incentives for using hydrogen as a sustainable and clean energy source. "Hydrogen economy" has been around since 1970s, but it started to look practicable only in recent years. The trend in the future is to switch from using hydrogen as the basic raw material in the chemical industry to the energy carrier in the transportation and distributed energy industries. To meet the expected rising demand, hydrogen has to be generated in a more cost-effective manner. As one of the most important operation units in the hydrogen production, a high performance hydrogen separation membrane system is essential to the coming hydrogen economy.; The project of hydrogen separation membrane based on Mixed ionic and electronic conductor (MIEC) composite was initiated by DoE years ago, and the MIEC membrane has been developed in Argonne National Laboratory (ANL) for several years. The goal at ANL is to develop a dense, ceramic-based MIEC membrane that is highly selective, chemical stable in practical environments at operative temperatures up to ≈900°C, and can separate hydrogen from mixed gases at commercially significant fluxes under industrially relevant operating conditions, without the need for electrodes or electrical circuitry.; The effort at ANL initially focused on BCY20 (BaCe0.8Y 0.2O3). BCY20 forms the matrix of ANL-1a and -2a ceramic-metal composite membranes (40-50 vol.% of a metal is dispersed in a ceramic matrix) and its bulk transport properties, including ionic transfer number, ionic and electronic conductivity, and chemical and mechanical stability have been systematically studied. However, exposure to CO2 and H2O-containing atmospheres, as would be present in a practical environment, will degrade the material as it reacts to form insulating barium carbonate (BaCO3 ) and cerium oxide (CeO2). This decomposition greatly limits its applicability in hydrogen separation, despite the promising properties of this material.; The combination of high proton conductivity and good chemical stability, which is a prerequisite for the application of MIEC compounds, is generally considered to be a key problem. In choosing good materials for H2 separation membrane, defect structure, and hence transport properties of perovskites, which are strongly influenced by the oxidation states and ionic radii of dopants, are very critical. Therefore it is the goal of this research to gain a fundamental understanding of the correlation between the defect chemistry and the properties of perovskite structure materials, so as to allow the engineering of these materials with the desired properties for the application in industry, such as developing membranes of mixed conductors which have good stability in practical atmospheres.; With respect to thermodynamic stability, water solubility limit and mobility of protonic defects the occupation of the A-site does not require much of a compromise. Except for the stability with acidic gases, which is almost independent of the choice of the A-cation, all relevant properties are superior for an A-site occupation by the big barium compared to other alkaline earth ions.; Addition of acceptor dopants into ABO3 is crucial to proton uptake. A high concentration of protonic defects requires a high acceptor dopants concentration. Dopants are incorporated into the lattice at either A or B-sites with the respective creation of charge-compensating oxygen vacancies and A-site vacancies. Smaller dopants preferentially substitute at the B-site, while larger cations substitute at the A-site. Partial occupation of the A sublattice can explain the low uptake of protons. The yttrium seems to be perfect acceptor dopant choice for BaZrO3, BaCeO3-based materials, and both the proton mobility and the thermodynamics of hydration are practically unchanged for dopant levels up to 20% Y.; The choice of the B-cation, however, requires some compromising. It should be of