ABSTRACT
New solid electrolytes are crucial for the development of all-solid-state lithium batteries with advantages in safety and energy densities over current liquid electrolyte systems. While some of the best solid-state Li+-ion conductors are based on sulfides, their air sensitivity makes them less commercially attractive, and attention is refocusing on air-stable oxide-based systems. Among these, the LISICON-structured systems, such as Li2+2xZn1-xGeO4 and Li3+xV1-xGexO4, have been relatively well studied. However, other systems such as the Li4GeO4-Li2MoO4 system, which also show LISICON-type structures, have been relatively little explored. In this work, the Li4-2xGe1-xMoxO4 solid solution is investigated systematically, including the solid solution limit, structural stability, local structure, and the corresponding electrical behavior. It is found that a γ-LISICON structured solution is formed in the range of 0.1 ≤ x < 0.4, differing in structure from the two end members, Li4GeO4 and Li2MoO4. With increasing Mo content, the ß-phase becomes increasingly more stable than the γ-phase, and at x = 0.5, a pure ß-phase (ß-Li3Ge0.5Mo0.5O4) is readily isolated. The structure of this previously unknown compound is presented, along with details of the defect structure of Li3.6Ge0.8Mo0.2O4 (x = 0.2) based on neutron diffraction data. Two basic types of defects are identified in Li3.6Ge0.8Mo0.2O4 involving interstitial Li+-ions in octahedral sites, with evidence for these coming together to form larger defect clusters. The x = 0.2 composition shows the highest conductivity of the series, with values of 1.11 × 10-7 S cm-1 at room temperature rising to 5.02 × 10-3 S cm-1 at 250 °C.
ABSTRACT
High-temperature fuel cells (namely, molten carbonate and solid oxide; MCFCs and SOFCs) require the cathode to be designed to maximize oxygen catalytic reduction, oxygen ion transport, electrical conductivity, and gas transport. This then leads to the optimization of the volume fraction and morphology of phases, as they are a pathway for electrons, ions, and gases to be continuous and self-interpenetrating. Apart from the functional properties, the cathode must be mechanically stable to prevent cracking during fuel cell assembly and operation. The manufacturing process of the composite cathode was optimized to meet such requirements in this research work. The tape casting technique and further firing process were used to fabricate the cathodes. The slurry for the green tape was composed of nickel (Ni), cerium oxide doped with samarium oxide (SDC), water (solvent), and an organic binder (which becomes pore space after firing). Each of these elements is necessary for the effective transport of specific species: electrons, oxygen, ions, and gas particles, respectively. Moreover, the nickel foam was embedded into the powder-based structure to improve mechanical strength. The study involved many technological issues, such as the effect of the SDC fraction on the cathode microstructure, mechanical strength, and chemical stability at high temperatures, and also involved environmental issues.
