A new family of electrolytes based on Na1/2Bi1/2TiO3 for intermediate-temperature solid oxide fuel cells

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A Solid Oxide Fuel Cell (SOFC) is an electrochemical device similar to a battery in that it consists of a cathode, anode and an electrolyte. They are solid-state devices where all components are ceramics and the electrolyte is an oxide-ion conductor. They operate at high temperatures (typically ~800C) where an electrochemical reaction converts fuel (eg H2, natural gas, biofuels) and air into electricity without combustion. They represent a leading direction for future power generation as they offer higher energy conversion efficiency (>60%) than conventional combustion engines (~30%) and lower pollution. Unfortunately, such high operating temperatures are costly and create engineering challenges such as long term sealing and durability of SOFCs. As a consequence, there is a drive within the SOFC community to reduce the operating temperatures to 500-700C (so called Intermediate Temperature SOFCs, ITSOFCs) to overcome the engineering challenges and reduce costs to produce clean, reliable and affordable energy. This requires the development of new electrolytes with high oxide-ion conductivity that can operate under the harsh operating conditions of simultaneous exposure to fuel and air at >500C. Rare earth (RE) stabilised d-Bi2O3 (eg RE=Er, ESB) are excellent solid electrolytes and offer sufficiently high oxide-ion conductivity at 500-700C in air but decompose under reducing conditions. One of the highest performances of an ITSOFC has been achieved using the concept of an electrolyte bilayer based on two oxide-ion conducting ceramics, Gadolinia-doped ceria (GDC) and ESB. Although the conductivity of GDC is lower than ESB it is chemically stable under reducing conditions. In this design, the GDC layer is placed at the heavily reducing anode (fuel) side to minimise the decomposition of ESB and the ESB layer is placed at the cathode (air) side. This provides a stable electrolyte with high ionic conductivity; however, preparation of such a bilayer requires a thin film deposition technique which is costly and impractical for mass production.Recently, we discovered high levels of oxide-ion conductivity in a well-known perovskite (Na1/2Bi1/2TiO3, NBT; Nature Materials, in press) and that chemical doping of Mg for Ti to increase the concentration of oxygen vacancies further enhanced the oxide-ion conductivity. Mg-doping has two other important advantages: Mg-NBT is chemically stable under reducing (fuel) conditions at 550 C and the sintering temperature of ~950C to obtain dense ceramics is similar to that of ESB and other d-(Bi,RE)2O3 electrolytes. Tape casting is a well-known technique for mass production of thick film ceramics at low cost. It is not possible to prepare GDC/ESB bilayers by tape casting followed by co-sintering due to the large difference in sintering temperature for GDC (~1350C) and ESB (~900C) ceramics; however, this should be possible for doped-NBT/ESB ceramics.The aims of this project are two-fold. First, to optimise the electrolyte properties of a newly discovered family of oxide-ion conductors based on the polar perovskite NBT. Second, to test the suitability of NBT-based materials as an electrolyte component in ITSOFCs based on bilayer electrolytes. The first aim will be achieved by undertaking systematic chemical doping studies of NBT followed by crystallographic, microstructural and electrical characterisation of doped-NBT ceramics. This will provide a comprehensive understanding of the structure-property-composition relationships of oxide-ion conductivity in this family of materials. To achieve the second aim, electrolyte bilayer ceramics will be produced by co-sintering tape-cast layers of doped-NBT and d-(Bi,RE)2O3 at temperatures < 1000C and their electrical and chemical performance tested under the conditions required for ITSOFCs. This will provide a proof-of-concept application of these materials in ITSOFCs based on bilayer electrolytes prepared by industry-standard tape casting technology.