Beta-alumina solid electrolyte

Beta-alumina solid electrolyte (BASE) is a fast ion conductor material used as a membrane in several types of molten salt electrochemical cell. There is no known substitute.

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β''-Alumina (beta prime-prime alumina) is an isomorphic form of aluminum oxide (Al₂O₃) a hard polycrystalline ceramic in which when prepared as an electrolyte is complexed with a mobile ion, which may be Na⁺, K⁺ , Li⁺ , Ag⁺ , H⁺ , Pb₂⁺ , Sr₂⁺ or Ba₂⁺ depending on the application. Beta-alumina is a good conductor of its mobile ion yet allows no non-ionized conductivity.

Sodium beta alumina is a non-stoichiometric sodium aluminate known for its rapid transport of Na⁺ ions. This material selectively passes sodium ions while containing all other liquids, including liquid sodium and liquid sulfur. It is a ceramic which can be formed and sintered by commercially available techniques and its conductivity at operating temperatures — 250 to 300 degrees Celsius — compares favorably with electrolytes used in conventional battery systems such as sulfuric acid and potassium hydroxide. The crystal structure of the Na-Al₂O₃ provides an essential rigid framework with channels along which the ionic species of the solid can migrate. Ion transport involves hopping from site to site along these channels.

BASE was first developed by researchers at the Ford Motor Company, in the search for a storage device for electric vehicles while developing the sodium-sulfur battery. The NaS battery consists of sulfur at positive electrode, sodium at negative electrode as active materials, and Beta alumina of sodium ion conductive ceramic which separates both electrodes. This hermetically sealed battery is kept at approximately 300 degrees Celsius and is operated under the condition that the active materials at both electrodes are liquid and its electrolyte is solid. At this temperature, since both active materials react smoothly, and internal resistance becomes low enough, the NaS battery has excellent performance. Because of reversible charging and discharging, the NaS battery can be continuously used. Several commercial installations use this type of battery for load leveling.

The sodium sulfur battery was a topic of intense worldwide interest during the 1970s and 1980s, but interest in the technology for vehicle use diminished for a variety of technical and economic reasons. In contrast, its "successor", the sodium nickel chloride battery, is now entering the commercialization phase. The sodium nickel chloride battery (or ZEBRA battery, so-called for the Zeolite Battery Research Africa Project) has been under development for almost 20 years. Y.F.Y. Yao and J.T. Kummer, J. Inorg. Nucl. Chem. 29 (1967) p. 2453

When BASE is used in a sodium nickel chloride (ZEBRA) cell, several requirements must be met. It must have a low resistivity, typically 4 cm at 350 °C, and a strength in excess of 200 MPa. It must be produced in the form of a thin-walled (1.25 mm), convoluted tube by low-cost production methods, and it must maintain a stable resistance in the cell for up to 10 years. These requirements have mostly been met by a variation of the sol-gel process.

BASE is also used in alkali-metal thermal to electric converters. (AMTEC) AMTEC is a high efficiency device for directly converting heat to electricity. AMTEC operates as a thermally regenerative electrochemical cell by expanding sodium through the pressure differential across the (BASE) membrane. BASE electrolytes have been used in some molten-carbonate fuel cells, as well as other liquid electrode/solid electrolyte fuel cell designs.

References

• Hybridization and Cogeneration with Concentrated Solar Radiation (CSR) Technology
• The alkali problem in the crystal structure of beta alumina
• BETA ALUMINA - PRELUDE TO A REVOLUTION IN SOLID STATE ELECTROCHEMISTRY