Inkjet Printing of PrBa0.5Sr0.5Co1.5Fe0.5O5+ δ Cathode for High-Performance Proton Ceramic Fuel Cells

Abstract

Ceramic fuel cells have been actively studied and are in the commercialization stage because of their economic and efficiency advantages, including the lack of precious metal catalysts, including Pt, fuel flexibility, and high efficiency. Solid oxide fuel cells (SOFCs) are the most typical type of ceramic fuel cell that conduct oxide ions. However, the operating temperature of SOFCs is high (>700 °C) owing to the high activation energy required for ion conduction. Prolonged operation at high temperatures can cause chemical and mechanical degradation in materials and peripheral parts, discouraging their use as long-time stationary generators, which is the main target market for SOFCs. For these reasons, expectations and interest in proton ceramic fuel cells (PCFCs) have recently increased owing to excellent power and durability exhibited at intermediate temperatures (<600 °C). According to recent reports, the durability of PCFC is superior to that of SOFC, even when methane fuel or city gas is used. The cathode reaction accounts for the highest resistance in PCFC operation. Therefore, the development of a high-performance cathode is the biggest factor for the success of PCFCs. To develop a high-performance cathode, the following factors must be optimized: 1) surface and interface shapes and components that can maximize the charge transfer reaction, and 2) porous microstructure that can effectively deliver oxygen gas to the reaction sites, and 3) electrolyte-electrode adhesion at the interface. The potential of inkjet printing (IJP) as a fabrication technology capable of optimizing these structures and components was recently confirmed by our group. IJP has attracted attention as a thin-film deposition technology that can produce complex and sophisticated microstructures, such as various multi-component ceramic materials, while controlling them at the nano-level. Recently, solution processes such as spin coating, tape casting, and screen printing have been frequently adopted in device manufacturing owing to their advantages such as simple accessibility and convenient management. However, fabricating films with nanoscale thickness is very difficult. Moreover, the precision with which a microstructure with the desired shape can be fabricated is limited. Conventional thin-film processes, such as physical vapor deposition and chemical vapor deposition, require complex and difficult deposition conditions, such as high-temperature or high-vacuum maintenance. In addition, equipment management is difficult, a large number of parts and a large system are required, and large-area deposition is highly challenging. Meanwhile, in the case of IJP technology, it is feasible to deposit high-quality nanoscale thin films relatively conveniently without requiring vacuum or temperature maintenance. Furthermore, they can be manufactured over large areas. IJP can be used to conveniently fabricate various patterns in the desired shape without masking or lithography. Moreover, it can precisely control the concentration and combination of printing inks to produce thin films with desired material compositions and microstructures. We successfully fabricated perovskite-type PBSCF cathodes for PCFCs using thermal inkjet printing (T-IJP) on a BaZrxCe0.8-xY0.1Yb0.1O3-δ electrolyte using an inexpensive desktop printer. Ceramic ink solutions were formulated using PBSCF nanopowder as a solid material and dispersed in anhydrous ethanol/propylene glycol methyl ether (PGME)-based solvents. The ink properties were improved by adding various polymers such as surfactants and dispersants. Printability was verified by analyzing the viscosity, surface tension, and particle size of the pigments. The shape and microstructure of the PBSCF cathode layer were successfully adjusted by controlling the number of printing cycles and grayscale value (color level) using commercial printing software. We verified the tendency of these specimens by observing the images using a scanning electron microscope (SEM) equipped with energy dispersive spectra. We also conducted performance evaluations and electrochemical impedance spectroscopy (EIS). Finally, we obtained an optimized PBSCF cathode (G-80) with adequate thickness and a favorable number of pores and cracks. The samples had identical thicknesses of 6–7 μm. This enabled a more reliable and accurate comparison and examination of the tendencies of the specimen microstructures by using grayscale values. We enhanced the performance compared to that of our previous T-IJP work. Among the four specimens measured in this study, G-80 attained a high power output of 728 mWcm-2 in the sub-IT regime (< 600 °C). This performance is higher than that achieved in previous similar studies.