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Reducing the operating temperature of Solid Oxide Fuel Cells (SOFCs) to 300–600 °C is a great challenge for the development of SOFC. Among the extensive research and development (R&D) efforts that have been done on lowering the operating temperature of SOFCs, nanomaterials have played a critical role in improving ion transportation in electrolytes and facilitating electrochemical catalyzation of the electrodes. This work reviews recent progress in lowering the temperature of SOFCs by using semiconductor-ionic conductor nanomaterial, which is typically a composition of semiconductor and ionic conductor, as a membrane. The historical development, as well as the working mechanism of semiconductor-ionic membrane fuel cell (SIMFC), is discussed. Besides, the development in the application of nanostructured pure ionic conductors, semiconductors, and nanocomposites of semiconductors and ionic conductors as the membrane is highlighted. The method of using nano-structured semiconductor-ionic conductors as a membrane has been proved to successfully exhibit a significant enhancement in the ionic conductivity and power density of SOFCs at low temperatures and provides a new way to develop low-temperature SOFCs.

Interface engineering can be used to tune the properties of heterostructure materials at an atomic level, yielding exceptional final physical properties. In this work, we synthesized a heterostructure of a p-type semiconductor (NiO) and an n-type semiconductor (CeO2) for solid oxide fuel cell electrolytes. The CeO2-NiO heterostructure exhibited high ionic conductivity of 0.2 S cm−1 at 530 °C, which was further improved to 0.29 S cm−1 by the introduction of Na+ ions. When it was applied in the fuel cell, an excellent power density of 571 mW cm−1 was obtained, indicating that the CeO2-NiO heterostructure can provide favorable electrolyte functionality. The prepared CeO2-NiO heterostructures possessed both proton and oxygen ionic conductivities, with oxygen ionic conductivity dominating the fuel cell reaction. Further investigations in terms of electrical conductivity and electrode polarization, a proton and oxygen ionic co-conducting mechanism, and a mechanism for blocking electron transport showed that the reconstruction of the energy band at the interfaces was responsible for the enhanced ionic conductivity and cell power output. This work presents a new methodology and scientific understanding of semiconductor-based heterostructures for advanced ceramic fuel cells.