Factors contributing to the breakdown of sodium beta-alumina

Clarification of the breakdown process occurring during charge transfer in sodium beta alumina solid electrolytes was derived from: (1) studying the effects of molten sodium contact at 350/sup 0/C on single crystal sodium beta alumina and polycrystalline sodium beta alumina; (2) determination of critical current density by monitoring acoustic emissions accompanying crack growth in sodium/sodium beta alumina/sodium cells subjected to linear current ramping at 1 mA cm/sup -2/ sec/sup -1/; (3) failure analysis conducted on cycled electrolytes, some from commercial sodium/sulfur cells, which had been subjected to up to 703 Ahr cm/sup -2/ of charge transfer. Gray coloration developing in beta aluminas in contact with molten sodium was found to be a consequence of formation, through reduction by sodium, of oxygen vacancies charge compensated by electrons. Electronic conductivity of the electrolyte increases as a result. No second phase formation was detected. Colored electrolytes from sodium/sulfur cells show evidence of a newly recognized degradation mechanism in which fracture occurs when sodium is reduced and deposited internally under pressure as metal in regions where an electronic conductivity gradient exists. Heating colored beta aluminas in air produces reoxidation and bleaching. Kinetics and other properties of the coloration and bleaching processes were determined. Critical current density was found to bear an inverse relation to average electrolyte grain size. Evidence was found in the cycled electrolytes for a slow crack growth mechanism and a progressive mode of degradation advancing from the sulfur electrode interface. Implications of the findings for the construction and operation of sodium/sulfur battery systems are discussed